Coloring agents and methods of use thereof

ABSTRACT

Dyes, compositions comprising dyes and methods for using the same are provided.

RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 61/288,668, filed on Dec. 21, 2009, 61/288,676, filed on Dec. 21,2009 and U.S. Provisional Patent Application No. 61/415,251, filed onNov. 18, 2010. The entire contents of the foregoing applications arehereby incorporated by reference.

BACKGROUND

According to the International Cosmetic Ingredient Dictionary andHandbook, Tenth Ed., 2004 (herein incorporated by reference in itsentirety) hair colorants (e.g., materials which impart color to hair)are classified as temporary, semi-permanent, permanent or progressive.

Temporary hair colorants include color rinses, which provide color thatlasts until the first shampooing. Ingredients which impart temporarycolor may have a fairly high molecular weight and are unable topenetrate the hair shaft. These materials are simply deposited onto thehair fiber and are removed by subsequent shampooing.

Direct dyes generally provide color through several shampooings. Thesematerials are either low molecular weight pre-formed colored compoundsthat can penetrate the hair shaft to some extent or larger molecularweight colored compounds that interact with the surface of the hairfiber via non-covalent interactions.

Oxidative dyes are considered permanent hair coloring preparations asthey provide color that is not substantially removed by shampooing.Oxidative coloration involves the deposition of an essentially colorlessintermediate and of a coupling agent inside the hair fiber. In thepresence of an oxidizing agent, usually hydrogen peroxide, thesechemicals form a series of complex colored dyestuffs inside the hairfiber. Progressive hair coloring preparations are oxidative hair colorswhich develop color gradually by repeated applications.

While oxidative dyes may be preferred due to their long-lastingcoloration, they have some disadvantages to direct coloringpreparations. For example, direct dyes are more vibrant and provide amore “pure” color than do the oxidative dyes. It will be appreciated bythose skilled in the art that the “pure” color of direct dyes is due togenerally higher extinction coefficients and narrower peak widths athalf height than oxidative dyes. Oxidative dyes can also participate inside reactions during the application process that can affect the finalhair color and perform less well on damaged hair. Therefore, it would bedesirable to develop non-oxidative dyes with the color and vibrancy of adirect dye and the long lasting color fastness of an oxidative dye thatoptionally performs better on damaged hair than on non-damaged hair.

SUMMARY OF THE INVENTION

The present invention is based, at least in part, on the discovery thatcertain functionalized, non-oxidative dyes exhibit an enhanced colorfastness and vibrancy compared to other dyes (e.g., oxidative dyesand/or direct dyes). Therefore, it is an object of the present inventionto provide such dyes and compositions thereof, as well as methods ofusing such dyes and kits comprising the same.

Accordingly, in one aspect, the present invention provides afunctionalized dye comprising at least one chromophore and a colorfastness moiety, wherein the chromophore is bound to the color fastnessmoiety by a linker, wherein said functionalized dye has an enhancedcolor fastness compared to a non-functionalized direct dye.

In some embodiments, the dye is a compound of formula Ia:

C-L-F   (Ia)

wherein

C is a chromophore;

L is a linker; and

F is a color fastness moiety, or a cosmetically acceptable salt thereof.

In some embodiments, color fastness moiety comprises at least onehydrogen bond donor and at least one hydrogen bond acceptor.

In some embodiments, the linker and the color fastness moiety comprisetwo or more hydrogen bond donors and at least one hydrogen bondacceptor.

In some embodiments, the hydrogen bond acceptor is a tertiary amine.

In some embodiments, the hydrogen bond donor is a secondary amine.

In some embodiments, C is of formula IIz:

wherein

R^(26a) is attached to linker L; and

R^(26b), R^(26c), R^(26d), R^(26e) and R^(26f) are each independentlyhydrogen, hydroxy, amino, alkoxy, alkyl, halogen, NO₂, CF₃, SO₃H, CN,aminocarbonyl, carbonyl, alkoxycarbonyl or an aryldiazene moiety.

In some embodiments, R^(26b) is —NO₂; R^(26c), R^(26e) and R^(26f) arehydrogen; R^(26d) is hydrogen or NH₂.

In some embodiments, L is of formula (III):

wherein

L covalently link the chromophore C via the left hand side of formulaIII to the color fastness moiety F via the right hand side of formulaIII;

a, b, c, d, e, and f are each independently an integer from 0-2,provided that at least one of a, b, c, d, e and f is not 0;

R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰ and R⁵¹ are eachindependently absent or hydrogen;

E is NR⁵² or NR⁵³C═O;

R⁵² and R⁵³ are each independently hydrogen or alkyl.

In some embodiments, a, b, c and d are each 0, e and f are each 1; E isNR⁵²; and R⁵² is hydrogen.

In some embodiments, the color fastness moiety is of formula (V):

wherein

m, n, o, p, q and r are each independently an integer from 0-2, providedthat at least one of m, n, o, p, q and r is not 0;

R⁷⁸, R⁷⁹, R⁸⁰, R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁷, R⁸⁸ and R⁸⁹ are eachindependently hydrogen or absent;

R⁸⁶ is absent, hydrogen or hydroxyl;

K is NR⁹⁰, C(═O)NR⁹² or OC═O;

W is NR⁹⁵R⁹⁶, CR⁹⁷R⁹⁸R⁹⁹ or OR¹⁰⁰;

R⁹⁰ and R⁹² are each independently hydrogen or alkyl;

R⁹⁵ is alkyl and R⁹⁶ is hydrogen or alkyl, or R⁹⁵ and R⁹⁶, together withthe nitrogen to which they are attached are linked to form a4-8-membered heterocyclic ring comprising 1-3 heteroatoms;

R⁹⁷, R⁹⁸ and R⁹⁹ are hydrogen, alkyl, alkoxy or heteroaryl; and

R¹⁰⁰ is hydrogen or alkyl, or a cosmetically acceptable salt thereof,

provided that when m, n, o and p are 0; q and r are 1, R⁸⁶, R⁸⁷, R⁸⁸ andR⁸⁹ are each hydrogen; W is OR¹⁰⁰, K is NR⁹⁰ and R¹⁰⁰ is hydrogen, thenR⁹⁰ is not methyl.

In some embodiments, m, n and o are 0; p, q and r are each 1; R⁸⁴, R⁸⁵,R⁸⁶, R⁸⁷; R⁸⁸ and R⁸⁹ are each hydrogen; K is NR⁹⁰; R⁹⁰ is hydrogen; Wis NR⁹⁵NR⁹⁶, and R⁹⁵ and R⁹⁶ are each alkyl.

In some embodiments, the dye is a compound of formula Xa:

wherein

R^(a), R^(b), R^(c), R^(d) and R^(e) are each independently hydrogen,hydroxy, amino, alkoxy, alkyl, halogen, NO₂, CF₃, SO₃H, CN,aminocarbonyl, carbonyl, alkoxycarbonyl or an aryldiazene moiety;

aa and bb are each an integer from 1-5;

A is NR^(f) or NR^(f)CO;

D is O(CO), NR^(g) or CONR^(g);

R^(f), R^(g) and R^(h) are each independently hydrogen or alkyl;

R^(i) is alkyl; or R^(h) and R^(i) are linked together with the atom towhich they are attached form a 4-8 membered heterocyclic ring with 1-3heteroatoms; or a cosmetically acceptable salt thereof.

In some embodiments, R^(a) is —NO₂; R^(b), R^(d) and R^(e) are eachhydrogen; R^(c) is hydrogen or NH₂; A is NR^(f); D is NR^(g); R^(f) andR^(g) are each hydrogen; and R^(h) and R^(i) are each alkyl. In someembodiments, the alkyl is methyl, ethyl or hydroxyethyl.

In some embodiments, R^(a) is —NO₂; R^(b), R^(d) and R^(e) are eachhydrogen; R^(c) is hydrogen or NH₂; A is NR^(f); D is NR^(g); R^(f) andR^(g) are each hydrogen; and R^(h) and R^(i) are linked to form a6-membered heterocyclic ring. In some embodiments, the ring is apiperidine or morpholine ring.

In some embodiments, the dye is a compound of formula (XIa):

R^(j) and R^(k) are each independently hydrogen, hydroxy, amino, alkoxy,alkyl, halogen, NO₂, CF₃, SO₃H, CN, aminocarbonyl, carbonyl,alkoxycarbonyl or an aryldiazene moiety;

cc and dd are each an integer from 1-5;

T is NR¹ or NR¹CO;

M is NR^(m) or CONR^(m);

Q is NR^(n)R^(o);

R^(l), R^(m) and R^(n) are each independently hydrogen or alkyl;

R^(o) is alkyl; or R^(n) and R^(o) are linked together with the atom towhich they are attached form a 4-8 membered heterocyclic ring with 1-3heteroatoms; and cosmetically acceptable salts thereof.

In some embodiments, T is NR^(l); M is NR^(m); R^(l) and R^(m) are eachhydrogen; cc is 2 and dd is 3; R^(j) is NO₂; R^(k) is hydrogen or NH₂;R^(n) and R^(o) are each alkyl. In some embodiments, the alkyl ismethyl, ethyl or hydroxyethyl.

In some embodiments, T is NR^(l); M is NR^(m); R^(l) and R^(m) are eachhydrogen; cc is 2 and dd is 3; R^(j) is NO₂; R^(k) is hydrogen or NH₂;R^(n) and R^(o) are linked to form a 6-membered heterocyclic ring. Insome embodiments, the ring is a piperidine or a morpholine ring.

In some embodiments, the dye is a compound of formula XII:

wherein

R^(p) is hydrogen or amino;

R^(q) and R^(r) are each independently hydrogen or alkyl;

ee and ff are each independently an integer from 1-5; and

R^(s) and R^(t) are each alkyl or together with the atom to which theyare attached form a 4-8 membered heterocyclic ring with 1 or 2heteroatoms, and cosmetically acceptable salts thereof.

In some embodiments, R^(q) and R^(r) are each hydrogen; ee is 2 and ffis 3; and R^(s) and R^(t) are each alkyl. In some embodiments, the alkylis methyl, ethyl or hydroxyethyl. In some embodiments, R^(p) is hydrogenor NH₂

In some embodiments, R^(q) and R^(r) are each hydrogen; ee is 2 and ffis 3; and R^(s) and R^(t) are linked to form a 6-membered heterocyclicring. In some embodiments, the ring is a piperidine or morpholine ring.In some embodiments, R^(p) is hydrogen or NH₂.

In some embodiments, the dye is a compound of formula XIII:

wherein

R^(u) is hydrogen or NH₂ and

R^(v) and R^(w) are alkyl, and cosmetically acceptable salts thereof.

In some embodiments, R^(v) and R^(w) are each methyl, ethyl orhydroxyethyl.

In some embodiments, the dye is a compound selected from Table 2 or acosmetically acceptable salt thereof.

In some aspects, the present invention provides a dye compositioncomprising at least one dye disclosed herein and a medium suitable fordyeing keratin fibers.

In some embodiments, the medium further includes one or more ofsurfactants, thickeners, direct dyes, fragrances, sequestering agents,UV-screening agents, waxes, silicones, preserving agents, couplers,primary intermediates, alkalizing agents, ceramides, oils, vitamins,provitamins, opacifiers, reducing agents, antioxidants, emulsifiers,chelating agents, color retardants, solvents and buffers.

In some aspects, the invention provides methods for coloring haircomprising applying to said hair a dye composition comprising at leastone dye disclosed herein, or a cosmetically acceptable salt thereof.

In some embodiments, the coloring hair is highlighting hair or touchingup roots.

In some aspects, the present invention provides a kit comprising a dyecomposition comprising at least one dye disclosed herein andinstructions for use.

In some embodiments, the kit further comprises at least one or moredirect dyes, a developer bottle, gloves or a conditioning rinse.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 a and 1 b compare the color fastness of a commercially availablered dye (FIG. 1 a) with the color fastness of compound A (FIG. 1 b)immediately after application to hair (1 a and 1 b; left tresses) andafter 15 shampoo cycles (1 a and 1 b; right tresses).

FIGS. 2 a and 2 b compare the color fastness of a commercially availablered dye applied to increasingly damaged hair (FIG. 2 a) with the colorfastness of compound A applied to tresses having the same damage (FIG. 2b) immediately after application to hair and after 15 shampoo cycles.The left tress of each pair is the initial color while the right tressof each pair is the result after shampooing. The last tress in both 2 aand b does not have a shampooing pair (only the initial color wasexamined).

DETAILED DESCRIPTION OF THE INVENTION

In order to more clearly and concisely describe the subject matter ofthe claims, the following definitions are intended to provide guidanceas to the meaning of terms used herein.

As used herein, the articles “a” and “an” mean “one or more” or “atleast one,” unless otherwise indicated. That is, reference to anyelement of the present invention by the indefinite article “a” or “an”does not exclude the possibility that more than one of the element ispresent.

I. Dyes

It should be noted that the terma “dye” and “compound” may be usedinterchangeably.

In some aspects, the present invention provides functionalized dyes. Thelanguage “functionalized dye” includes dyes having at least onechromophore that has been chemically modified. The language“non-functionalized dye” includes dyes that have at least onechromophore that has not been chemically modified. In some embodiments,the non-functionalized dye is a chromophore, C, as defined below.

In other aspects, the present invention provides damage selective dyes.The language “damage selective dye” includes dyes that perform better ondamaged hair than normal hair (e.g., undamaged hair). The term “damagedhair” includes hair that is more porous than normal hair due to chemicalexposure (e.g., bleaching or overdying hair, exposure to chemicals inswimming pools or minerals in groundwater), prolonged or repeated heatexposure (e.g., through the use of heat styling tools or excessive sunexposure), prolonged UV exposure, excessive perming and straightening ofhair or a genetic predisposition to having more porous hair. In oneembodiment, damaged hair includes hair with split ends. The language“normal hair” includes hair that is of normal porosity (e.g., undamagedhair) and may include unbleached or uncolored hair.

In some aspects, invention provides non-oxidative dyes. The language“non-oxidative dye” includes dyes that are pre-formed before applicationon the hair and do not require a coupling agent or an oxidizing agent toform the dye after deposition on the hair. In contrast, the language“oxidative dye” includes dyes that are formed by the application of anintermediate, a coupling agent and an oxidizing agent onto the hair suchthat the intermediate and coupling agent penetrate the hair and undergoa chemical reaction to form a colored dye within the hair.

In some embodiments, the dyes of the invention have a greater colorfastness than a semi-permanent dye (e.g., a level 2 dye or a dye thatlasts for about 5-8 shampoos). In some embodiments, the dyes of theinvention have a greater color fastness than a permanent (e.g., a level3 dye or a dye that last for about 9 or more shampoos). The language“greater color fastness” includes the ability of the dye to have animproved resistance to color change or color fading after application tohair when compared to a direct dye or an oxidative dye of substantiallythe same color.

In some embodiments, the dye is retained and imparts color on hair afterapplication to the hair. The language “retained and imparts color”includes the ability of the dye to remain on the hair and provide thedesired color with substantially no change in color or fading of colorafter a period of time compared to a direct dye or an oxidative dye ofsubstantially the same color and after substantially the same period oftime, as measured by the visual inspection assay described in Example 4.In some embodiments, the dye is retained and imparts color on hair afterapplication to the hair at least about 5%, about 10%, about 15%, about20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%,about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about85%, about 90%, about 95% or about 100% longer than a direct dye or anoxidative dye of substantially the same color.

In other embodiments, the dye has greater vibrancy after application tohair. The language “greater vibrancy” includes the ability of the dye toprovide a brighter color after application to hair compared to anoxidative dye, as measured, for example, by the visual inspection assaydescribed in Example 4 or by a colorimeter. In some embodiments, the dyeprovides vibrancy that is about 5%, about 10%, about 15%, about 20%,about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%,about 90%, about 95% or about 100% greater than an oxidative dye ofsubstantially the same color.

In other embodiments, the dye maintains its vibrancy after applicationto hair. The language “maintains vibrancy” includes the ability of thedye to retain its brightness after a period of time compared to anoxidative dye of substantially the same color after substantially thesame period of time, as measured by the visual inspection assaydescribed in Example 4. In some embodiments, the dye maintains itsvibrancy by about 5%, about 10%, about 15%, about 20%, about 25%, about30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%,about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about95% or about 100% longer than an oxidative dye of substantially the samecolor.

In some embodiments, the dyes of the invention are non-ionic (e.g., thedyes do not have a positive charge (e.g., non-cationic) or negativecharge (e.g., non-anionic)). Examples of anionic and cationic dyesinclude, but are not limited to, those in Table 1.

In some embodiments, the dye is fluorescent.

In other embodiments, the dye is a non-natural dye (e.g., a dye obtainedfrom a natural source, for example, a plant, animal or mineral).Examples of dyes obtained from natural sources include, for example,indigo, carminic acid, lawsone (e.g., henna), lycopene, madder, monascusderivatives, santalin, annatto, apigenin, canthaxanthin, capsanthin,capsorubin, carotenes, carthamin, crocin, crocetin, curcumin, lutein,luteolin, pratol, caramel, cocoa, chlorophyll and indigo.

In still other embodiments and without being bound by theory, the dyeinteracts with hair by non-covalent interactions after application tothe hair. Examples of non-covalent interactions include, for example,hydrogen bonding, pi stacking, van der Waals interactions, hydrophobicinteractions and dipole-dipole interactions.

In some embodiments, the dye is a functionalized oxidative dye precursoror intermediate that is capable of further reactive chemistry inside thehair fiber typical of oxidative dyes (e.g., functionalizedpara-phenylene diamine) such that the final reacted dye has longerlasting color than the non-functionalized dye.

In one embodiment, the dye is of formula Ia:

C-L-F   (Ia)

wherein

C is a chromophore,

L is a linker and;

F is a color fastness moiety and cosmetically acceptable salts thereof.

In other embodiments, the dye is of formula Ib:

C-L-F-L*-C*   (Ib)

wherein

C and C* are each the same or a different chromophores;

L and L* are linkers; and

F is a color fastness moiety, and cosmetically acceptable salts thereof.

The term “chromophore” includes chemical moieties that are capable ofproviding color to the dyes of the invention. In some embodiments, thechromophore is a colored moiety prior to being covalently linked to Land/or L* and/or F. In other embodiments, the dye resulting fromcovalently linking L and/or L* and/or F to C or C* when C or C* is acolored moiety provides a molecule with the same or a different colorthan C or C*. In some embodiments, when C or C* are non-coloredmolecules, the covalent bonding of C or C* to L and/or L* and/or Fresult in a colored molecule.

In some embodiments, the chromophore (e.g., C or C*) is selected fromthe group consisting of an anthraquinone chromophore, an arylmethanechromophore, a diarylmethane chromophore, a diphenyl methanechromophore, a triarylmethane chromophore, an azo chromophore, a cyaninechromophore, a diazonium chromophore, a nitro chromophore, a nitrosochromophore, a phthalocyanine chromophore, a quinone-imine chromophore,an azin chromophore, an eurhodin chromophore, a safranin chromophore, anindamin chromophore, an indophenol chromophore, an oxazin chromophore,an oxazone chromophore, a thiazin chromophore, a thiazole chromophore, axanthene chromophore, a fluorine chromophore, a pyronin chromophore, afluorine chromophore, a rhodamine chromophore, a substituted benzene ora derivative or a cosmetically acceptable salts thereof. Examples of theforegoing chromophores include, but are not limited to, those compoundsfound in Table 1.

In at least one embodiment, the present invention includes dyes whereinthe “C” or “C*” substitutent of formulae Ia and Ib is a knownchromophore, e.g., including, but not limited to, a chromophore listedin Table 1, below. In this embodiment, the dyes of the invention includean “L” or “L*”substituent and/or and “F” substituent, which are definedabove, in addition to the chromophores. In another embodiment, the dyeof the invention is not a compound of Table 1.

In other embodiments, the chromophore is a compound of formula IIa:

wherein

R^(1a), R^(1b), R^(1c), R^(1d), R^(1e), R^(1f), R^(1g), R^(1h), R^(1i),R^(1j), R^(1k), R^(1l), R^(1m), R^(1n), R^(1o) and R^(1p) are eachindependently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino,alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen,acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety or thioetheror are attached to linker L or L*, and cosmetically acceptable saltsthereof.

In other embodiments, the chromophore is a compound of formula IIb:

wherein

R^(2a), R^(2b), R^(2c), R^(2d), R^(2e), R^(2f), R^(2g), R^(2h), R^(2i),R^(2j), R^(2k), R^(2l), R^(2m) and R^(2n) are each independentlyhydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium,sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl,hydrazinyl, —NO₂, —CN, a heterocyclic moiety or thioether or areattached to the linker L or L*, and cosmetically acceptable saltsthereof.

In other embodiments, the chromophore is a compound of formula IIc:

wherein

R^(3a), R^(3b), R^(3c), R^(3d), R^(3e), R^(3f), R^(3g), R^(3h), R^(3i),R^(3j), R^(3k), R^(3l), R^(3m), R^(3n), R^(3o) and R^(3p) are eachindependently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino,alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen,acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety or thioetheror are attached to linker L or L*, and cosmetically acceptable saltsthereof.

In other embodiments, the chromophore is a compound of formula IId:

wherein

R^(4a), R^(4b), R^(4c), R^(4d), R^(4e), R^(4f), R^(4g), R^(4h), R^(4i),R^(4j), R^(4k), R^(4l), R^(4m), R^(4n), R^(4o), R^(4p), R^(4q) andR^(4r) are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy,alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, aheterocyclic moiety or thioether or are attached to linker L or L*, andcosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIe:

wherein

R^(5a), R^(5b), R^(5c), R^(5d), R^(5e), R^(5f), R^(5g), R^(5h), R^(5i),R^(5k), R^(5l), R^(5m), R^(5n), R^(5o), R^(5p), R^(5q), R^(5r), R^(5s),R^(5t), R^(5u), R^(5w) and R^(5x) are each independently hydrogen,hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl,carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl,—NO₂, —CN, a heterocyclic moiety or thioether or are attached to linkerL or L*; and

R^(5j) and R^(5v) are each independently hydrogen, hydroxyl, alkoxy,alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl or are attachedto the linker L or L*, and cosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIf:

wherein

R^(6a), R^(6b), R^(6c), R^(6d), R^(6e), R^(6f), R^(6g), R^(6h), R^(6i),R^(6j), R^(6k), R^(6l), R^(6m) and R^(6n) are each independentlyhydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium,sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl,hydrazinyl, —NO₂, —CN, a heterocyclic moiety or thioether or areattached to linker L or L*, and cosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIg:

wherein

R^(7a), R^(7b), R^(7c), R^(7d), R^(7e), R^(7f), R^(7g), R^(7h), R^(7i)and R^(7j) are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy,alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, aheterocyclic moiety or thioether or are attached to linker L or L*, andcosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIh:

wherein

R^(8a), R^(8b), R^(8c), R^(8d), R^(8e), R^(8f), R^(8g), R^(8h), R^(8i),R^(8j), R^(8k) and R^(8l) are each independently hydrogen, hydroxyl,alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl,carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN,a heterocyclic moiety or thioether or are attached to linker L or L*,and cosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula Ili:

wherein

R^(9a), R^(9b), R^(9c), R^(9d), R^(9e), R^(9f), R^(9g), R^(9h), R^(9i),R^(9j), R^(9k) and R^(9l) are each independently hydrogen, hydroxyl,alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl,carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN,a heterocyclic moiety or thioether or are attached to linker L or L*,and cosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIj:

wherein

R^(10a), R^(10b), R^(10c), R^(10d), R^(10e), R^(10f), R^(10g), R^(10h),R^(10i), R^(10j), R^(10k), R^(10l), R^(10m) and R^(10n) are eachindependently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino,alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen,acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety or thioetheror are attached to linker L or L*, and cosmetically acceptable saltsthereof.

In other embodiments, the chromophore is a compound of formula IIk:

wherein

R^(11a), R^(11b), R^(11c), R^(11d), R^(11e), R^(11f), R^(11g), R^(11h),R^(11i), R^(11j), R^(11l) and R^(11m) are each independently hydrogen,hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl,carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl,—NO₂, —CN, a heterocyclic moiety or thioether or are attached to linkerL or L*; and

R^(11k) is hydrogen, hydroxyl, alkoxy, alkyl, alkenyl, alkynyl, aryl,carbonyl, carboxy, acyl or is attached to linker L or L*, andcosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIl:

wherein

R^(12b), R^(12d), R^(12e), R^(12f), R^(12g), R^(12h) and R^(12i) areeach independently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl,amino, alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether or are attached to linker L or L*; and

R^(12a) and R^(12d) are each independently hydrogen, hydroxyl, alkoxy,alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl or are attachedto linker L or L*, and cosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIm:

wherein

R^(13a), R^(13b), R^(13c), R^(13d), R^(13e), R^(13f), R^(13g), R^(13h),R^(13i), R^(13j), R^(13k) and R^(13l) are each independently hydrogen,hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl,carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl,—NO₂, —CN, a heterocyclic moiety or thioether or are attached to linkerL or L*, and cosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIn:

wherein

R^(14a), R^(14b), R^(14c), R^(14d), R^(14e), R^(14f), R^(14g), R^(14j),R^(14k), R^(14l), R^(14m), R^(14n), R^(14o) and R^(14p) are eachindependently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino,alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen,acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety or thioetheror are attached to linker L or L*; and

R^(14h) and R^(14i) are each independently hydrogen, hydroxyl, alkoxy,alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl or are attachedto linker L or L*, and cosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIo:

wherein

R^(15a), R^(15b), R^(15c), R^(15d), R^(15e), R^(15f), R^(15g), R^(15j),R^(15k), R^(15l), R^(15m), R^(15n), R^(15o), R^(15p), R^(15q) andR^(15r) are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy,alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, aheterocyclic moiety or thioether or are attached to linker L or L*; and

R^(15h) and R^(15i) are each independently hydrogen, hydroxyl, alkoxy,alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl or are attachedto linker L or L*, and cosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIp:

wherein

R^(16a), R^(16b), R^(16c), R^(16d), R^(16e) and R^(16f) are eachindependently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino,alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen,acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety or thioetheror are attached to linker L or L*, and cosmetically acceptable saltsthereof.

In other embodiments, the chromophore is a compound of formula IIq:

wherein

R^(17a), R^(17b), R^(17c), R^(17d), R^(17e), R^(17f), R^(17g) andR^(17h) are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy,alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, aheterocyclic moiety or thioether or are attached to the linker L or L*,and cosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIr:

wherein

R^(18a), R^(18b), R^(18c), R^(18d), R^(18e), R^(18h), R^(18i), R^(18j),R^(18k), R^(18l) and R^(18m) are each independently hydrogen, hydroxyl,alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl,carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN,a heterocyclic moiety or thioether or are attached to linker L or L*;and

R^(18g) and R^(18n) are each independently hydrogen, hydroxyl, alkoxy,alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl or are attachedlinker L or L*, and cosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIs:

wherein

R^(19a), R^(19b), R^(19c), R^(19d), R^(19e), R^(19g), R^(19h), R^(19j),R^(19k), R^(19l), R^(19m), R^(19o), R^(19p), R^(19r), R^(19s), R^(19t),R^(19u), R^(19v), R^(19w), R^(19x), R^(19y), R^(19z), R^(19a*),R^(19b*), R^(19c*) and R^(19d*) are each independently hydrogen,hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl,carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl,—NO₂, —CN, a heterocyclic moiety or thioether or are attached to linkerL or L*; and

R^(19f), R^(19i), R^(19n) and R^(19q) are each independently hydrogen,hydroxyl, alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acylor are attached to linker L or L*, and cosmetically acceptable saltsthereof.

In other embodiments, the chromophore is a compound of formula IIt:

wherein

R^(20a), R^(20b), R^(20c), R^(20d), R^(20e), R^(20g), R^(20h), R^(20j),R^(20k), R^(20l), R^(20m), R^(20n), R^(20o) and R^(20p) are eachindependently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino,alkylammonium, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy, halogen,acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety or thioetheror are attached to linker L or L*; and

R^(20f) and R^(20i) are each independently hydrogen, hydroxyl, alkoxy,alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl or are attachedto linker L or L*, and cosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIu:

wherein

R^(21a), R^(21b), R^(21c), R^(21d), R^(21e), R^(21f), R^(21g), R^(21h),R^(21i), R^(21j), R^(21k) and R^(21l) are each independently hydrogen,hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl,carbonyl, carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl,—NO₂, —CN, a heterocyclic moiety or thioether or are attached to linkerL or L*;

P is O or NR^(21m); and

R^(21m) is hydrogen, hydroxyl, alkoxy, alkyl, alkenyl, alkynyl, aryl,carbonyl, carboxy, acyl or is attached to linker L or L*, andcosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIv:

wherein

R^(22a), R^(22b), R^(22c), R^(22d), R^(22e), R^(22g), R^(22h), R^(22i),R^(22j), R^(22k) and R^(22l) are each independently hydrogen, hydroxyl,alkyl, alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl,carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN,a heterocyclic moiety or thioether or are attached to linker L or L*;and

R^(22f) is hydrogen, alkyl, alkenyl, alkynyl, aryl, carbonyl, acyl or aheterocyclic moiety or is attached to L or L*, and cosmeticallyacceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIw:

wherein

R^(23a), R^(23b), R^(23c), R^(23d), R^(23f), R^(23g), R^(23h) andR^(23i) are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy,alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, aheterocyclic moiety or thioether or are attached to linker L or L*;

Q is S, O or N;

T is N⁺R^(23e) or N when R^(23e) is absent; and

R^(23e) is absent, hydrogen, hydroxyl, alkoxy, alkyl, alkenyl, alkynyl,aryl, carbonyl, carboxy, acyl or is attached to linker L or L*, andcosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIx:

wherein

R^(24a), R^(24b), R^(24c), R^(24d), R^(24e), R^(24f), R^(24h), R^(24i),R^(24j) and R^(24k) are each independently hydrogen, hydroxyl, alkyl,alkenyl, alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl,carboxy, alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN,a heterocyclic moiety or thioether or are attached to linker L or L*;

U is N⁺R^(24g) or O when R^(24g) is absent; and

R^(24g) is absent, hydrogen, hydroxy, alkoxy, alkyl, alkenyl, alkynyl,aryl, carbonyl, carboxy, acyl or is attached to linker L or L*, andcosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIy:

wherein

R^(25a), R^(25b), R^(25c), R^(25d), R^(25e), R^(25f), R^(25h), R^(25i)and R^(25j) are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, alkylammonium, sulfonyl, carbonyl, carboxy,alkoxy, aryloxy, halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, aheterocyclic moiety or thioether or are attached to the linker L or L*;

V is CR^(25i)R^(25j) or NR^(25k); and

R^(25g) and R^(25k) are each independently hydrogen, hydroxyl, alkoxy,alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl or attached to Lor L*, and cosmetically acceptable salts thereof.

In other embodiments, the chromophore is a compound of formula IIz:

wherein

R^(26a), R^(26b), R^(26c), R^(26d), R^(26e) and R^(26f) are eachindependently hydrogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, amino,alkylammonium, sulfonyl, sulfonic acid, carbonyl, carboxy, alkoxy,aryloxy, halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, —CF₃, SO₃H,aminocarbonyl, alkoxycarbonyl, a heterocyclic moiety, a diazene orthioether or are attached to the linker L or L*, and cosmeticallyacceptable salts thereof.

In some embodiments, the C is of formula IIz:

wherein

R^(26a) is attached to linker L; and

R^(26b), R^(26c), R^(26d), R^(26e) and R^(26f) are each independentlyhydrogen, hydroxy, amino, alkoxy, alkyl, CF₃, CN, halogen, NO₂, SO₃H,aminocarbonyl, carbonyl, alkoxycarbonyl or an aryldiazene moiety.

In some embodiments, R^(26b) is —NO₂.

In some embodiments, R^(26c), R^(26e) and R^(26f) are hydrogen.

In some embodiments, R^(26d) is hydrogen or NH₂.

In yet other embodiments, the chromophore (e.g., C or C*) includes, butis not limited to, Acid Blue 1, Acid Blue 3, Acid Blue 5, Acid Blue 7,Acid Blue 9, Acid Blue 62, Acid Blue 104, Acid Brown 13, Acid Orange 3,Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, AcidOrange 20, Acid Orange 24, Acid Red 14, Acid Red 33, Acid Red 35, AcidRed 41, Acid Red 50, Acid Red 51, Acid Red 52, Acid Red 87, Acid Red 92,Acid Red 94, Acid Red 95, Acid Red 98, Acid Red 184, Acid Green 1, AcidGreen 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Yellow 1,Acid Yellow 9, Acid Yellow 73, Acid Violet 9, Acid violet 50, Basic Blue3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue41, Basic Blue 47, Basic Blue 99, Basic Brown 4, Basic Brown 16, BasicBrown 17, Basic Green 1, Basic Green 4, Basic Orange 1, Basic Orange 2,Basic Orange 31, Basic Red 1, Basic Red 2, Basic Red 22, Basic Red 46,Basic Red 51, Basic Red 76, Basic Red 118, Basic Violet 1, Basic Violet2, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 11,Basic Violet 14, Basic Violet 16, Basic Yellow 11, Basic Yellow 28,Basic Yellow 40, Basic Yellow 57, Basic Yellow 87, Direct Black 51,Direct Red 23, Direct Red 80, Direct Red 81, Direct Violet 48, DirectYellow 12, Disperse Black 9, Disperse Blue 1, Disperse Blue 3, DisperseBlue 7, Disperse Blue 72, Disperse Brown 1, Disperse Orange 3, DisperseRed 1, Disperse Red 3, Disperse Red 11, Disperse Red 13, Disperse Red14, Disperse Red 15, Disperse Red 17, Disperse Red 19, Disperse Violet1, Disperse Violet 4, Disperse Violet 15, Disperse Violet 27, HC Blue 2,HC Blue 4, HC Blue 5, HC Blue 6, HC Blue 8, HC Blue 9, HC Blue 10, HCBlue 11, HC Blue 12, HC Blue 13, HC Blue 14, HC Blue 15, HC Brown 1, HCBrown 2, HC Green 1, HC Orange 1, HC Orange 2, HC Orange 3, HC Orange 5,HC Red 1, HC Red 3, HC Red 7, HC Red 8, HC Red 9, HC Red 10, HC Red 11,HC Red 13, HC Red 14, HC Violet 1, HC Violet 2, HC Yellow 2, HC Yellow4, HC Yellow 5, HC Yellow 6, HC Yellow 7, HC Yellow 8, HC Yellow 9, HCYellow 10, HC Yellow 11, HC Yellow 12, HC Yellow 13, HC Yellow 14, HCYellow 15, Disperse Red 3, Disperse Red 19, Acid Black 1, Acid Red 1,Acid Red 73, Solvent Red 23, Scarlet Red, Brilliant Black 1, Brown 1, CI20040, CI 21100, CI 21108, CI 21230, CI 27755, CI 28440, Acid Black 52,Acid Red 18, Acid Red 27, Lithol Rubin B, Betanine, Lithol Red, CI15800, CI 15880, Hansa Red B, CI 12085, Pigment Red 22, CI 15865:2, CI16155, Acid Red 26, CI 14700, Solvent Orange 7, Acid Red 88, CI 11680,CI 11710, CI 11725, CI 11920, CI 12010, CI 12085, CI 12120, CI 12150, CI12370, CI 12420, CI 12480, CI 12490, Acid Yellow 23, Acid Red 195, CI12700, CI 14700, CI 14815, CI 15525, CI 15580, CI 15630, CI 15850, CI15980, CI 15985, CI 16035, Acid Red 155, Acid Yellow 121, Acid Red 180,Acid Yellow 11, CI 12075, CI 12100, CI 42053, Acid Violet 43, CI 69825,Solvent Blue 63, CI 58000, CI 61565, Acid Blue 80, CI 69800, CI 10006,Rhodamine B, Japan Red 104, Japan Red 223, Acid Yellow 73, CI 45396, CI45410, CI 45370, CI 51319 and a compound disclosed of Table 1, and/orderivatives and cosmetically acceptable salts thereof.

TABLE 1

and cosmetically acceptable salts thereof.

In one embodiment, the color fastness moiety (e.g., F) of formulae Iaand Ib is linked (e.g., covalently bound) to the chromophore (e.g., Cand C*) via a linker (e.g., L and L*, respectively). The term “linker”includes chemical moieties that are capable of linking (e.g., by acovalent bond) the chromophore to the color fastness moiety.

In some embodiments, the linker has at least one hydrogen bond donormoiety. In some embodiments, the color fastness moiety has at least onehydrogen bond donor moiety and at least one hydrogen bond acceptormoiety. In some embodiments, the color fastness moiety together with thelinker comprise at least one hydrogen bond donor and at least onehydrogen bond acceptor. In some embodiments, the color fastness moietytogether with the linker comprise at least 2 hydrogen bond donors and atleast one hydrogen bond acceptor.

The language “hydrogen bond donor moiety” includes those chemical groupsthat have a hydrogen covalently bonded to an electronegative atom, forexample, oxygen, nitrogen, fluorine, and the like. In some embodiments,the hydrogen bond donor moiety is a hydroxyl or a primary (e.g., —NH₂)or secondary amino moiety (e.g., —NHR).

The language “hydrogen bond acceptor moiety” includes electronegativeatoms that have lone pair of electrons with which to interactnon-covalently with the hydrogen of the hydrogen bond donor. Examples ofhydrogen bond acceptor moieties include oxygen, nitrogen and fluorine.In some embodiments, the hydrogen bond acceptor moiety is a primary,secondary or tertiary amino moiety (e.g., —NR₂), a hydroxyl moiety, anether moiety (e.g., —R—O—R) or CF₃.

In some embodiments, the linker and the colorfastness moiety togetherhave at least three amino moieties. In some embodiments, at least one ofthe amino moieties is a tertiary amine.

In other embodiments, linker L is of formula III:

wherein

L covalently links C via the left hand portion of formula III to F viathe right hand side of formula III;

E is NR⁵², O, S, SO₂, SO₃, C=A, NR⁵³C=A, C(=A)NR⁵⁴, NR⁵⁵C(=A)NR⁵⁶,(C=A)O, OC=A or

A, A* and A** are each independently oxygen or sulfur;

Y is NR¹²⁵, O, S, SO₂, SO₃, C=A*, NR¹²⁶C=A*, C(=A*)NR¹²⁷,NR¹²⁸C(=A*)NR¹²⁹, (C=A*)O or OC=A*;

Z is NR¹³⁰, O, S, SO₂, SO₃, C=A**, NR¹³¹C=A**, C(=A**)NR¹³²,NR¹³³C(=A**)NR¹³⁴, (C=A**)O or OC=A**;

a, b, c, d, e, f , v, w and x are each independently an integer between0 and 5, provided that at least one of a, b, c, d, e, f, v, w and x isnot 0;

R⁴⁰ and R⁴¹ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁴⁰ and R⁴¹ are absent when a is 0;

R⁴² and R⁴³ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁴² and R⁴³ are absent when b is 0;

R⁴⁴ and R⁴⁵ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁴⁴ and R⁴⁵ are absent when c is 0;

R⁴⁶ and R⁴⁷ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁴⁶ and R⁴⁷ are absent when d is 0;

R⁴⁸ and R⁴⁹ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁴⁸ and R⁴⁹ are absent when e is 0;

R⁵⁰ and R⁵¹ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁵⁰ and R⁵¹ are absent when f is 0;

R¹¹⁹ and R¹²⁰ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R¹¹⁹ and R¹²⁰ are absent when v is 0;

R¹²¹ and R¹²² are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R¹²¹ and R¹²² are absent when w is 0;

R¹²³ and R¹²⁴ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R¹²³ and R¹²⁴ are absent when x is 0; or

R⁴⁰ and R⁴¹ or R⁴¹ and R⁴² or R⁴² and R⁴³ or R⁴³ and R⁴⁴ or R⁴⁴ and R⁴⁵or R⁴⁵ and R⁴⁶ or R⁴⁶ and R⁴⁷ or R⁴⁷ and R⁴⁸ or R⁴⁸ and R⁴⁹ or R⁴⁹ andR⁵⁰ or R⁵⁰ and R⁵¹ or R¹¹⁹ and R¹²⁰ or R¹²⁰ and R¹²¹ or R¹²¹ and R¹²² orR¹²³ and R¹²⁴, together with the carbon atoms to which they are attachedare linked to form a 3 to 10-membered carbocyclic or heterocyclic ring;

R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R¹²⁵, R¹²⁶, R¹²⁷, R¹²⁸; R¹²⁹; R¹³⁰, R¹³¹, R¹³²,R¹³³ and R¹³⁴ are each independently hydrogen, hydroxy, alkoxy, alkyl,alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl or NR⁵⁷R⁵⁸; and

R⁵⁷ and R⁵⁸ are each independently hydrogen, alkyl, alkenyl, alkynyl,aryl, a heterocyclic moiety or carbonyl.

In some embodiments, the linker L is of formula IIIa:

wherein

L covalently links C via the left hand side of formula IIIa to F via theright hand side of formula IIIa;

a, b, c, d, e, and f are each independently an integer from 0-2,provided that at least one of a, b, c, d, e and f is not 0;

R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰ and R⁵¹ are eachindependently absent or hydrogen;

E is NR⁵² or NR⁵³C═O;

R⁵² and R⁵³ are each independently hydrogen or alkyl.

In some embodiments, a, b, c and d are each 0.

In some embodiments, e and f are each 1.

In some embodiments, E is NR⁵².

In some embodiments, R⁵² is hydrogen.

In some embodiments, R⁵² is alkyl (e.g., ethyl).

In other embodiments, L* is of formula IV:

wherein

L* is covalently bound to C* via the left hand side of formula IV;

G is NR⁷¹, O, S, SO₂, SO₃, C=J, NR⁷²C=J, C(=J)NR⁷³, NR⁷⁴C(=J)NR⁷⁵,(C=J)O, OC=J or

J, J* and J** is oxygen or sulfur;

Y* is NR¹⁴¹, O, S, SO₂, SO₃, C=J*, NR¹⁴²C=J*, C(=J*)NR¹⁴³,NR¹⁴⁴C(=J*)NR¹⁴⁵, (C=J*)O or OC=J*;

Z* is NR¹⁴⁶, O, S, SO₂, SO₃, C=J**, NR147C=J**, C(=J**)NR¹⁴⁸,NR¹⁴⁹C(=J**)NR¹⁵⁰, (C=J**)O, OC=J** or

g, h, i, j, k, l, v*, w* and x* are each independently an integerbetween 0 and 5, provided that at least one of g, h, I, j, k, l, v*, w*and x* is not 0;

R⁵⁹ and R⁶⁰ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁵⁹ and R⁶⁰ are absent when g is 0;

R⁶¹ and R⁶² are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁶¹ and R⁶² are absent when h is 0;

R⁶³ and R⁶⁴ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁶³ and R⁶⁴ are absent when i is 0;

R⁶⁵ and R⁶⁶ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁶⁵ and R⁶⁶ are absent when j is 0;

R⁶⁷ and R⁶⁸ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁶⁷ and R⁶⁸ are absent when k is 0;

R⁶⁹ and R⁷⁰ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁶⁹ and R⁷⁰ are absent when l is 0;

R¹³⁵ and R¹³⁶ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R¹³⁵ and R¹³⁶ are absent when v* is 0;

R¹³⁷ and R¹³⁸ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R¹³⁷ and R¹³⁸ are absent when w* is 0;

R¹³⁹ and R¹⁴⁰ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R¹³⁹ and R¹⁴⁰ are absent when x* is 0; or

R⁵⁹ and R⁶⁰ or R⁶⁰ and R⁶¹ or R⁶¹ and R⁶² or R⁶² and R⁶³ or R⁶³ and R⁶⁴or R⁶⁴ and R⁶⁵ or R⁶⁵ and R⁶⁶ or R⁶⁶ and R⁶⁷ or R⁶⁷ and R⁶⁸ or R⁶⁸ andR⁶⁹ or R⁶⁹ and R⁷⁰ or R¹³⁵ and R¹³⁶ or R¹³⁶ and R¹³⁷ or R¹³⁷ and R¹³⁸ orR¹³⁸ and R¹³⁹ or R¹³⁹ and R¹⁴⁰, together with the carbon atoms to whichthey are attached are linked to form a 3 to 10-membered carbocyclic orheterocyclic ring;

R⁷¹, R⁷², R⁷³, R⁷⁴, R⁷⁵, R¹⁴¹, R¹⁴², R¹⁴³, R¹⁴⁴, R¹⁴⁵, R¹⁴⁶ R¹⁴⁷, R¹⁴⁸,R¹⁴⁹ and R¹⁵⁰ are each independently hydrogen, hydroxy, alkoxy, alkyl,alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl or NR⁷⁶R⁷⁷; and

R⁷⁶ and R⁷⁷ are each independently hydrogen, alkyl, alkenyl, alkynyl,aryl, a heterocyclic moiety or carbonyl.

The language, “color fastness moiety” includes chemical groups thatenable the dye to resist color change, e.g., a chemical group thatenhances the retention and/or stability of the dye on/in the substanceto which it is applied.

In one embodiment, the color fastness moiety is of formula V:

wherein

K is NR⁹⁰, O, S, SO₂, SO₃, C=M, NR⁹¹C=M, C(=M)NR⁹², NR⁹³C(=M)NR⁹⁴ or(C=M)O, OC=M when the dye is of formula Ia; or K is NL*, NL*C=M,C(=M)NL*, NL*C(=M)NR⁹⁴ or NR⁹³C(=M)NL* when the dye is of formula Ib;

W is NR⁹⁵R⁹⁶, CR⁹⁷R⁹⁸R⁹⁹, OR¹⁰⁰, SR¹⁰¹ or halogen,

M is oxygen or sulfur

m, n, o, p, q and r are independently an integer between 0 and 5,provided at least one of m, n, o, p, q, and r is not 0;

R⁷⁸ and R⁷⁹ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁷⁸ and R⁷⁹ are absent when m is 0;

R⁸⁰ and R⁸¹ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁸⁰ and R⁸¹ are absent when n is 0;

R⁸² and R⁸³ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁸² and R⁸³ are absent when o is 0;

R⁸⁴ and R⁸⁵ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁸⁴ and R⁸⁵ are absent when p is 0;

R⁸⁶ and R⁸⁷ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁸⁶ and R⁸⁷ are absent when q is 0;

R⁸⁸ and R⁸⁹ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R⁸⁸ and R⁸⁹ are absent when r is 0; or

R⁷⁸ and R⁷⁹ or R⁷⁹ and R⁸⁰ or R⁸⁰ and R⁸¹ or R⁸¹ and R⁸² or R⁸² and R⁸³or R⁸³ and R⁸⁴ or R⁸⁴ and R⁸⁵ or R⁸⁵ and R⁸⁶ or R⁸⁶ and R⁸⁷ or R⁸⁷ andR⁸⁸ or R⁸⁸ and R⁸⁹, together with the carbon atoms to which they areattached are linked to form a 3 to 10-membered carbocyclic orheterocyclic ring;

R⁹⁰, R⁹¹, R⁹², R⁹³ and R⁹⁴ are each independently hydrogen, hydroxy,alkoxy, alkyl, alkenyl, alkynyl, aryl, carbonyl, carboxy or acyl;

R⁹⁵ and R⁹⁶ are each independently hydrogen, hydroxy, alkoxy, alkyl,alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl or NR¹⁰²R¹⁰³, or R⁹⁵ andR⁹⁶ together with the nitrogen to which they are attached are linked toform a 3-10 membered aliphatic, heterocyclic or aromatic ring;

R⁹⁷, R⁹⁸ and R⁹⁹ are each independently hydrogen, hydroxyl, alkyl,alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy,aryloxy, halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclicmoiety or thioether, or R⁹⁷ and R⁹⁸ together with the carbon to whichthey are attached are linked to form a 3-10 membered carbocyclic orheterocyclic ring; or R⁹⁹ is absent and R⁹⁷ and R⁹⁸ together with thecarbon to which they are attached are linked to form a 4 to 10 memberedaromatic ring;

R¹⁰⁰ and R¹⁰¹ are each independently hydrogen, alkyl, alkenyl, alkynyl,aryl, carbonyl, acyl or a heterocyclic moiety; and

R¹⁰² and R¹⁰³ are each independently hydrogen, hydroxy, alkoxy, alkyl,alkenyl, alkynyl, aryl, carbonyl, carboxy or acyl, or R¹⁰² and R¹⁰³together with the nitrogen to which they are attached are linked to forma 3-10 membered aliphatic, heterocyclic or aromatic ring.

In some embodiments, color fastness moiety is of formula (Va):

wherein

m, n, o, p, q and r are each independently an integer from 0-2, providedthat at least one of m, n, o, p. q and r is not 0;

R⁷⁸, R⁷⁹, R⁸⁰, R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸ and R⁸⁹ are eachindependently hydrogen or absent;

R⁸⁶ is absent, hydrogen or hydroxyl;

K is NR⁹⁰, C(═O)NR⁹² or OC═O;

W is NR⁹⁵R⁹⁶, CR⁹⁷R⁹⁸R⁹⁹ or OR¹⁰⁰;

R⁹⁰ and R⁹² are each independently hydrogen or alkyl;

R⁹⁵ is alkyl and R⁹⁶ is hydrogen or alkyl, or R⁹⁵ and R⁹⁶, together withthe nitrogen to which they are attached are linked to form a4-8-membered heterocyclic ring comprising 1-3 heteroatoms;

R⁹⁷, R⁹⁸ and R⁹⁹ are hydrogen, alkyl, alkoxy or heteroaryl; and

R¹⁰⁰ is hydrogen or alkyl,

provided that when m, n, o and p are 0; q and r are 1, R⁸⁶, R⁸⁷, R⁸⁸ andR⁸⁹ are each hydrogen; W is OR¹⁰⁰, K is NR⁹⁰ and R¹⁰⁰ is hydrogen, thenR⁹⁰ is not methyl.

In some embodiments, m, n and o are 0.

In some embodiments, p, q and r are each 1.

In some embodiments, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷; R⁸⁸ and R⁸⁹ are each hydrogen.

In some embodiments, K is NR⁹⁰.

In some embodiments, R⁹⁰ is hydrogen.

In some embodiments, W is NR⁹⁵NR⁹⁶, and R⁹⁵ and R⁹⁶ are each alkyl.

In one embodiment, the dye is of formula Ia, and C is an azo dye. In yetanother embodiment, C is of formula IIg; R^(7a), R^(7b), R^(7d), R^(7e),R^(7f), R^(7g) and R^(7i) are each hydrogen; R^(7h) is —NO₂; R^(7j) ishalogen (e.g., chlorine) and R^(7c) is attached to L; a, b, c, d and eare each 0; E is NR⁵²; R⁵² is alkyl (e.g., ethyl); f is 1; R⁵⁰ and R⁵¹are each hydrogen; m, n and o are each 0; K is C(=M)NR⁹²; M is oxygen;p, q and r are each 1; R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁸⁹ and R⁹² are eachhydrogen; W is NR⁹⁵R⁹⁶; R⁹⁵ and R⁹⁶ are each alkyl (e.g., substituted orunsubstituted alkyl, for example, ethyl or hydroxyl substituted alkyl,such as hydroxyethyl).

In one embodiment, the dye is of formula Ia, and C is an azo dye. In yetanother embodiment, C is of formula IIg; R^(7a), R^(7b), R^(7d), R^(7e),R^(7f), R^(7g) and R^(7i) are each hydrogen; R^(7h) is —NO₂; R^(7j) ishalogen (e.g., chlorine) and R^(7c) is attached to L; a, b, c, d and eare each 0; E is NR⁵²; R⁵² is alkyl (e.g., ethyl); f is 1; R⁵⁰ and R⁵¹are each hydrogen; m, n and o are each 0; K is C(=M)NR⁹²; M is oxygen;p, q and r are each 1; R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁸⁹ and R⁹² are eachhydrogen; W is NR⁹⁵R⁹⁶; R⁹⁵ and R⁹⁶ are linked to form a ring (e.g., a6-membered heterocyclic ring, for example, a morpholinyl ring).

In one embodiment, the dye is of formula Ia, and C is an azo dye. In yetanother embodiment, C is of formula IIg; R^(7a), R^(7b), R^(7d), R^(7e),R^(7f), R^(7g) and R^(7i) are each hydrogen; R^(7h) is —NO₂; R^(7j) ishalogen (e.g., chlorine) and R^(7c) is attached to L; a, b, c, d and eare each 0; E is NR⁵²; R⁵² is alkyl (e.g., ethyl); f is 1; R⁵⁰ and R⁵¹are each hydrogen; m, n and o are each 0; K is C(=M)NR⁹²; M is oxygen;p, q and r are each 1; R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁸⁹ and R⁹² are eachhydrogen; W is CR⁹⁷R⁹⁸R⁹⁹; R⁹⁷ is hydrogen and R⁹⁸ and R⁹⁹ are eachalkoxy (e.g., ethoxy).

In one embodiment, the dye is of formula Ia, and C is an azo dye. In yetanother embodiment, C is of formula IIg; R^(7a), R^(7b), R^(7d), R^(7e),R^(7f), R^(7g) and R^(7i) are each hydrogen; R^(7h) is —NO₂; R^(7j) ishalogen (e.g., chlorine) and R^(7c) is attached to L; a, b, c, d and eare each 0; E is NR⁵²; R⁵² is alkyl (e.g., ethyl); f is 1; R⁵⁰ and R⁵¹are each hydrogen; m, n and o are each 0; K is C(=M)NR⁹²; M is oxygen;p, q and r are each 1; R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁸⁹ and R⁹² are eachhydrogen; W is CR⁹⁷R⁹⁸R⁹⁹; R⁹⁷ and R⁹⁸ are each hydrogen and R⁹⁹ ishydroxyl.

In one embodiment, the dye is of formula Ia, and C is an azo dye. In yetanother embodiment, C is of formula IIg; R^(7a), R^(7b), R^(7d), R^(7e),R^(7f), R^(7g) and R^(7i) are each hydrogen; R^(7h) is —NO₂; R^(7j) ishalogen (e.g., chlorine) and R^(7c) is attached to L; a, b, c, d and eare each 0; E is NR⁵²; R⁵² is alkyl (e.g., ethyl); f is 1; R⁵⁰ and R⁵¹are each hydrogen; m, n and o are each 0; K is C(=M)NR⁹²; M is oxygen;p, q and r are each 1; R⁸⁴, R⁸⁵, R⁸⁷, R⁸⁸, R⁸⁹ and R⁹² are eachhydrogen; R⁸⁶ is hydroxyl; W is OR¹⁰⁰ and R¹⁰⁰ is hydrogen.

In one embodiment, the dye is of formula Ia, and C is an azo dye. In yetanother embodiment, C is of formula IIg; R^(7a), R^(7b), R^(7d), R^(7e),R^(7f), R^(7g) and R^(7i) are each hydrogen; R^(7h) is —NO₂; R^(7j) ishalogen (e.g., chlorine) and R^(7c) is attached to L; a, b, c and d areeach 0; E is

Y is NR¹²⁵, R¹²⁵ is alkyl (e.g., ethyl); v and w are each 1; x is 0;R¹¹⁹, R¹²⁰, R¹²¹ and R¹²² are each hydrogen; Z is OC=A**; A** is oxygen;e and f are each 1; R⁴⁸, R⁴⁹, R⁵⁰ and R⁵¹ are each hydrogen; m, n and oare each 0; K is NR⁹⁰; p, q and r are each 1; R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸,R⁸⁹ and R⁹⁰ are each hydrogen; W is NR⁹⁵R⁹⁶; R⁹⁵ and R⁹⁶ are each alkyl(e.g., substituted or unsubstituted alkyl, for example ethyl or hydroxylsubstituted alkyl, such as hydroxyethyl).

In one embodiment, the dye is of formula Ia, and C is an azo dye. In yetanother embodiment, C is of formula IIg; R^(7a), R^(7b), R^(7d), R^(7e),R^(7f), R^(7g) and R^(7i) are each hydrogen; R^(7h) is —NO₂; R^(7j) ishalogen (e.g., chlorine) and R^(7c) is attached to L; a, b, c and d areeach 0; E is

Y is NR¹²⁵, R¹²⁵ is alkyl (e.g., ethyl); v and w are each 1; x is 0;R¹¹⁹, R¹²⁰, R¹²¹ and R¹²² are each hydrogen; Z is OC=A**; A** is oxygen;e and f are each 1; R⁴⁸, R⁴⁹, R⁵⁰ and R⁵¹ are each hydrogen; m, n and oare each 0; K is NR⁹⁰; p, q and r are each 1; R⁸⁴, R⁸⁵, R⁸⁷, R⁸⁸, R⁸⁹and R⁹⁰ are each hydrogen; R⁸⁶ is hydroxyl; W is OR¹⁰⁰; and R¹⁰⁰ ishydrogen.

In one embodiment, the dye is of formula Ia, and C is an azo dye. In yetanother embodiment, C is of formula IIg; R^(7a), R^(7b), R^(7d), R^(7e),R^(7f), R^(7g) and R^(7i) are each hydrogen; R^(7h) is —NO₂; R^(7j) ishalogen (e.g., chlorine) and R^(7c) is attached to L; a, b, c and d areeach 0; E is

Y is NR¹²⁵, R¹²⁵ is alkyl (e.g., ethyl); v and w are each 1; x is 0;R¹¹⁹, R¹²⁰, R¹²¹ and R¹²² are each hydrogen; Z is OC=A**; A** is oxygen;e and f are each 1; R⁴⁸, R⁴⁹, R⁵⁰ and R⁵¹ are each hydrogen; m, n and oare each 0; K is NR⁹⁰; p is 1; q is 1; r is 0; R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷ andR⁹⁰ are each hydrogen; W is NR⁹⁵R⁹⁶; R⁹⁵ and R⁹⁶ are each hydrogen.

In one embodiment, the dye is of formula Ia, and C is an azo dye. In yetanother embodiment, C is of formula IIg; R^(7a), R^(7b), R^(7d), R^(7e),R^(7f), R^(7g) and R^(7i) are each hydrogen; R^(7h) is —NO₂; R^(7j) ishalogen (e.g., chlorine) and R^(7c) is attached to L; a, b, c and d areeach 0; E is

Y is NR¹²⁵, R¹²⁵ is alkyl (e.g., ethyl); v and w are each 1; x is 0;R¹¹⁹, R¹²⁰, R¹²¹ and R¹²² are each hydrogen; Z is OC=A**; A** is oxygen;e and f are each 1; R⁴⁸, R⁴⁹, R⁵⁰ and R⁵¹ are each hydrogen; m, n and oare each 0; K is NR⁹⁰; p, q and r are each 1; R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸,R⁸⁹ and R⁹⁰ are each hydrogen; W is CR⁹⁷R⁹⁸R⁹⁹; R⁹⁷ is hydrogen and R⁹⁸and R⁹⁹ are each alkoxy (e.g., ethoxy).

In one embodiment, the dye is of formula Ib in which C and C* are thesame chromophore; C is of formula IIg, R^(7a), R^(7b),R^(7d),R^(7e),R^(7f), R^(7g) and R^(7i) are each hydrogen; R^(7h) is—NO₂; R^(7j) is halogen (e.g., chlorine); R^(7c) is attached to linkerL; a, b and c are 0; E is

Y is NR¹²⁵; R¹²⁵ is alkyl (e.g., ethyl); v and w are each 1; x is 0;R¹¹⁹, R¹²⁰, R¹²¹ and R¹²² are each hydrogen; Z is oxygen; d, e and f areeach 1; R⁴⁶, R⁴⁷, R⁴⁸, R⁵⁰ and R⁵¹ are each hydrogen; R⁴⁹ is hydroxyl;m, n and o are each 0; K is NL*; g, h and i are each 1; R⁵⁹, R⁶⁰, R⁶¹,R⁶³ and R⁶⁴ are each hydrogen; R⁶² is hydroxyl; G is

Y* is oxygen; v* is 1; w* is 1; x* is 0; R¹³⁵, R¹³⁶, R¹³⁷ and R¹³⁸ areeach hydrogen; Z* is NR¹⁴⁶; R¹⁴⁶ is alkyl (e.g., ethyl); j, k and l areeach 0; C* is of formula IIg in which R^(7a), R^(7b), R^(7d), R^(7e),R^(7f), R^(7g) and R^(7i) are each hydrogen; R^(7h) is —NO₂; R^(7j) ishalogen (e.g., chlorine); R^(7c) is attached to linker L*; p, q and rare each 1; R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸ and R⁸⁹ are each hydrogen; W isNR⁹⁵R⁹⁶; and R⁹⁵ and R⁹⁶ are each alkyl (e.g., hydroxyl substitutedalkyl, for example, hydroxyethyl).

In one embodiment, the dye is of formula Ib in which C and C* are thesame chromophore; C is of formula IIg, R^(7a), R^(7b), R^(7d), R^(7e),R^(7f), R^(7g) and R^(7i) are each hydrogen; R^(7h) is —NO₂; R^(7j) ishalogen (e.g., chlorine); R^(7c) is attached to linker L; a, b and c are0; E is

v is 1; w is 1; x is 0; R¹¹⁹, R¹²⁰, R¹²¹ and R¹²² are each hydrogen; Yis NR¹²⁵; R¹²⁵ is alkyl (e.g., ethyl); Z is oxygen; d, e and f are each1; R⁴⁶, R⁴⁷, R⁴⁸, R⁵⁰ and R⁵¹ are each hydrogen; R⁴⁹ is hydroxyl; m, nand o are each 0; K is NL*; g, h and i are each 1; R⁵⁹, R⁶⁰, R⁶¹, R⁶³and R⁶⁴ are each hydrogen; R⁶² is hydroxyl; G is

Y* is oxygen; v* is 1; w* is 1; x* is 0; _(R) ¹³⁵, R¹³⁶, R¹³⁷ and R¹³⁸are each hydrogen; Z* is NR¹⁴⁶; R¹⁴⁶ is alkyl (e.g., ethyl); j, k and lare each 0; C* is of formula IIg in which R^(7a), R^(7b), R^(7d),R^(7e), R^(7f), R^(7g) and R^(7i) are each hydrogen; R^(7h) is —NO₂;R^(7j) is halogen (e.g., chlorine); R^(7c) is attached to linker L*; p,q and r are each 1; R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁸ and R⁸⁹ are each hydrogen; R⁸⁷ ishydroxyl; W is OR¹⁰⁰ and R¹⁰⁰ is hydrogen.

In one embodiment, the dye is of formula Ib in which C and C* are thesame chromophore; C is of formula IIg, R^(7a), R^(7b), R^(7d), R^(7e),R^(7f), R^(7g) and R^(7i) are each hydrogen; R^(7h) is —NO₂; R^(7j) ishalogen (e.g., chlorine); R^(7c) is attached to linker L; a, b, c and dare 0; E is

v is 1; w is 1; x is 0; R¹¹⁹, R¹²⁰, R¹²¹ and R¹²² are each hydrogen; Yis NR¹²⁵; R¹²⁵ is alkyl (e.g., ethyl); Z is OC=A**; A** is oxygen; e andf are each 1; R⁴⁸, R⁴⁹, R⁵⁰ and R⁵¹ are each hydrogen; m, n and o areeach 0; K is NL*; g, and h are each 1; i is 0; R⁵⁹, R⁶⁰, R⁶¹ and R⁶² ,are each hydrogen; G is

Y* is (C=J*)O; J* is oxygen; v* is 1; w* is 1; x* is 0; R¹³⁵, R¹³⁶, R¹³⁷and R¹³⁸ are each hydrogen; Z* is NR¹⁴⁶; R¹⁴⁶ is alkyl (e.g., ethyl); j,k and l are each 0; C* is of formula IIg in which R^(7a), R^(7b),R^(7d), R^(7e), R^(7f), R^(7g) and R^(7i) are each hydrogen; R^(7h) is—NO₂; R^(7j) is halogen (e.g., chlorine); le is attached to linker L*;p, q and r are each 1; R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸ and R⁸⁹ are eachhydrogen; W is NR⁹⁵R⁹⁶; and R⁹⁵ and R⁹⁶ are each alkyl (e.g., ethyl orhydroxyethyl).

In one embodiment, the dye is of formula Ia; C is of formula IIz;R^(26b), R^(26e) and R^(26f) are each hydrogen; R^(26d) is amino (e.g.,arylamino, for example, phenylamino); R^(26c) is NO₂; R^(26a) isattached to linker L; a, b, c, and d are each 0; E is NR⁵³C=A; A isoxygen; e and f are each 1; R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹ and R⁵³ are eachhydrogen; m, n and o are each 0; K is NR⁹⁰; p, is 0; q and r are each 1;R⁸⁷, R⁸⁸, R⁸⁹ and R⁹⁰ are each hydrogen; W is OR¹⁰⁰; R¹⁰⁰ is hydrogen;and R⁸⁶ is alkyl (e.g., hydroxymethyl).

In one embodiment, the dye is of formula Ia; C is of formula IIz;R^(26b), R^(26e) and R^(26f) are each hydrogen; R^(26d) is amino (e.g.,arylamino, for example, phenylamino); R^(26c) is NO₂; R^(26a) isattached to linker L; a, b, c, and d are each 0; E is NR⁵³C=A; A isoxygen; e and f are each 1; R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹ and R⁵³ are eachhydrogen; m, n and o are each 0; K is NR⁹⁰; p is 1; q is 1; r is 0; R⁸⁴,R⁸⁵, R⁸⁶, R⁸⁷ and R⁹⁰ are each hydrogen; W is NR⁹⁵R⁹⁶; R⁹⁵ and R⁹⁶ areeach hydrogen or alkyl (e.g., hydroxyethyl).

In one embodiment, the dye is of formula Ia; C is of formula IIz;R^(26b), R^(26e) and R^(26f) are each hydrogen; R^(26d) is amino (e.g.,arylamino, for example, phenylamino); R^(26c) is NO₂; R^(26a) isattached to linker L; a, b, c, and d are each 0; E is NR⁵³C=A; A isoxygen; e and f are each 1; R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹ and R⁵³ are eachhydrogen; m, n and o are each 0; K is NR⁹⁰; p, q and r are each 1; R⁸⁴,R⁸⁵, R⁸⁷, R⁸⁸, R⁸⁹ and R⁹⁰ are hydrogen; R⁸⁶ is hydroxyl; W is OR¹⁰⁰ andR¹⁰⁰ is hydrogen.

In one embodiment, the dye is of formula Ia; C is of formula IIz;R^(26b), R^(26e) and R^(26f) are each hydrogen; R^(26d) is amino (e.g.,arylamino, for example, phenylamino); R^(26c) is NO₂; R^(26a) isattached to linker L; a, b, c, and d are each 0; E is NR⁵³C=A; A isoxygen; e and f are each 1; R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹ and R⁵³ are eachhydrogen; m, n and o are each 0; K is NR⁹⁰; p, q and r are each 1; R⁸⁴,R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁸⁹ and R⁹⁰ are each hydrogen; W is NR⁹⁵R⁹⁶; R⁹⁵ andR⁹⁶ are each alkyl (e.g., ethyl or hydroxyethyl).

In one embodiment, the dye is of formula Ia; C is of formula IIz;R^(26b), R^(26e) and R^(26f) are each hydrogen; R^(26d) is amino (e.g.,arylamino, for example, phenylamino); R^(26c) is NO₂; R^(26a) isattached to linker L; a, b, c, and d are each 0; E is NR⁵³C=A; A isoxygen; e and f are each 1; R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹ and R⁵³ are eachhydrogen; m, n and o are each each 0; K is NR⁹⁰; p, q and r are each 1;R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁸⁹ and R⁹⁰ are each hydrogen; W is CR⁹⁷R⁹⁸R⁹⁹;R⁹⁷ is hydrogen; R⁹⁸ and R⁹⁹ are each alkoxy (e.g., ethoxy).

In one embodiment, the dye is of formula Ia; C is of formula IIz;R^(26b), R^(26e) and R^(26f) are each hydrogen; R^(26d) is amino (e.g.,arylamino, for example, phenylamino); R^(26c) is NO₂; R^(26a) isattached to linker L; a, b, c, and d are each 0; E is NR⁵³C=A; A isoxygen; e and f are each 1; R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹ and R⁵³ are eachhydrogen; m, n and o are each 0; K is NR⁹⁰; p, q and r are each 1; R⁸⁴,R⁸⁵, R⁸⁶, R⁸⁷, R⁸⁸, R⁸⁹ and R⁹⁰ are each hydrogen; W is CR⁹⁷R⁹⁸R⁹⁹; R⁹⁷and R⁹⁸ are each hydrogen; R⁹⁹ is alkyl (e.g., n-butyl).

In some embodiments, C is of formula Hz; R^(26a) is attached to linkerL; R^(26b) is —NO₂; R^(26c), R^(26d), R^(26e) and R^(26f) are hydrogen;a, b, c and d are each 0; E is NR⁵²; e and f are each 1; R⁴⁸, R⁴⁹, R⁵⁰,R⁵¹ and R⁵² are each hydrogen; m, n and o are 0; K is NR⁹⁰; p, q and rare each 1; W is NR⁹⁵R⁹⁶; R⁹⁵ and R⁹⁶ are each alkyl (e.g., methyl,ethyl or hydroxyethyl); and R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷; R⁸⁸, R⁸⁹ and R⁹⁰ areeach hydrogen.

In some embodiments, C is of formula Hz, R^(26a) is attached to linkerL; R^(26b) is —NO₂; R^(26c), R^(26e) and R^(26f) are hydrogen; R^(26d)is —NH₂; a, b, c and d are each 0; E is NR⁵²; e and f are each 1; R⁴⁸,R⁴⁹, R⁵⁰, R⁵¹ and R⁵² are each hydrogen; m, n and o are 0; K is NR⁹⁰; p,q and r are each 1; W is NR⁹⁵R⁹⁶; R⁹⁵ and R⁹⁶ are each alkyl (e.g.,methyl, ethyl or hydroxyethyl); and R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷; R⁸⁸, R⁸⁹ and R⁹⁰are each hydrogen.

In some embodiments, C is of formula Hz; R^(26a) is attached to linkerL; R^(26b) is —NO₂; R^(26c), R^(26d), R^(26e) and R^(26f) are hydrogen;a, b, c and d are each 0; E is NR⁵²; e and f are each 1; R⁴⁸, R⁴⁹, R⁵⁰,R⁵¹ and R⁵²are each hydrogen; m, n and o are 0; K is NR⁹⁰; p, q and rare each 1; W is NR⁹⁵R⁹⁶; R⁹⁵ and R⁹⁶ are linked to form a 6-memberedheterocyclic ring (e.g., a piperidine or morpholine ring); and R⁸⁴, R⁸⁵,R⁸⁶, R⁸⁷; R⁸⁸, R⁸⁹ and R⁹⁰ are each hydrogen.

In some embodiments, C is of formula Hz, R^(26a) is attached to linkerL; R^(26b) is —NO₂; R^(26c), R^(26e) and R^(26f) are hydrogen; R^(26d)is —NH₂; a, b, c and d are each 0; E is NR⁵²; e and f are each 1; R⁴⁸,R⁴⁹, R⁵⁰, R⁵¹ and R⁵² are each hydrogen; m, n and o are 0; K is NR⁹⁰; p,q and r are each 1; W is NR⁹⁵R⁹⁶; R⁹⁵ and R⁹⁶ are linked to form a6-membered heterocyclic ring (e.g., a piperidine or morpholine ring);and R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷; R⁸⁸, R⁸⁹ and R⁹⁰ are each hydrogen.

In some embodiments, the dye is a compound of formula X:

wherein

R^(a), R^(b), R^(c), R^(d) and R^(e) are each independently hydrogen,hydroxy, amino, alkoxy, alkyl, CF₃, CN, halogen, NO₂, CF₃, SO₃H, CN,aminocarbonyl, carbonyl, alkoxycarbonyl or an aryldiazene moiety;

aa and bb are each an integer from 1-5;

A is O, S, CO, NR^(f), NR^(f)CO or CONR^(f);

D is O, S, CO, O(CO), NR^(g), NR^(g)CO or CONR^(g);

J is OR^(h), SR^(h) or NR^(h)R^(i);

R^(f), R^(g), and R^(h) are each independently hydrogen or alkyl;

R^(i) is alkyl; or R^(h) and R^(i) are linked together with the atom towhich they are attached form a 4-8 membered heterocyclic ring with 1-3heteroatoms; and cosmetically acceptable salts thereof, and

provided that when A is NR^(f); D is NR^(g); J is OR^(h); R^(a), R^(b),R^(e), R^(f) and R^(h) are each hydrogen; R^(c) is methylamino; R^(d) is—NO₂; aa is 3 and bb is 2, then R^(g) is not methyl.

In some embodiments, R^(a) is —NO₂, R^(b), R^(d) and R^(e) are eachhydrogen; R^(c) is amino (e.g., —NH₂); A is NR^(f), R^(f) is hydrogen,aa is 2, D is NR^(g), R^(g) is hydrogen; bb is 3; J is NR^(h)R^(i) andR^(h) and R^(i) are each alkyl (e.g., ethyl).

In some embodiments, R^(a) is —NO₂, R^(b), R^(c), R^(d) and R^(e) areeach hydrogen; A is NR^(f), R^(f) is hydrogen, aa is 2, D is NR^(g),R^(g) is hydrogen; bb is 3; J is NR^(h)R^(i) and R^(h) and R^(i) areeach alkyl (e.g., ethyl or hydroxyethyl).

In some embodiments, the dye is of formula Xa:

wherein

R^(a), R^(b), R^(c), R^(d) and R^(e) are each independently hydrogen,hydroxyl, amino, alkoxy, alkyl, CF₃, CN, halogen, NO₂, CF₃, SO₃H, CN,aminocarbonyl, carbonyl, alkoxycarbonyl or an aryldiazene moiety;

aa and bb are each an integer from 1-5;

A is NR^(f) or NR^(f)CO;

D is O(CO), NR^(g) or CONR^(g);

R^(f), R^(g) and R^(h) are each independently hydrogen or alkyl;

R^(i) is alkyl; or R^(h) and R^(i) are linked together with the atom towhich they are attached form a 4-8 membered heterocyclic ring with 1-3heteroatoms; or a cosmetically acceptable salt thereof.

In some embodiments, R^(a) is —NO₂.

In some embodiments, R^(b), R^(d) and R^(e) are each hydrogen.

In some embodiments, R^(c) is hydrogen or NH₂.

In some embodiments, A is NR^(f).

In some embodiments, D is NR^(g).

In some embodiments, R^(f) and R^(g) are each hydrogen.

In some embodiments, R^(h) and R^(i) are each alkyl (e.g., methyl, ethylor hydroxyethyl).

In some embodiments, R^(h) and R^(i) are linked to form a 6-memberedheterocyclic ring (e.g., a piperidine or morpholine ring).

In some embodiments, the dye is a compound of formula XI:

R^(j) and R^(k) are each independently hydrogen, hydroxyl, amino,alkoxy, alkyl, CF₃, CN, halogen, NO₂, CF₃, SO₃H, CN, aminocarbonyl,carbonyl, alkoxycarbonyl or an aryldiazene moiety;

cc and dd are each an integer from 1-5;

T is O, S, CO, NR^(l), NR^(l)CO or CONR^(l);

M is O, S, CO, OC(O), NR^(m), NR^(m)CO or CONR^(m);

Q is OR^(n), SR^(n) or NR^(n)R^(o);

R^(l), R^(m) and R^(n) are each independently hydrogen or alkyl;

R^(o) is alkyl; or R^(n) and R^(o) are linked together with the atom towhich they are attached form a 4-8 membered heterocyclic ring with 1-3heteroatoms; and cosmetically acceptable salts thereof.

In some embodiments, R^(j) is —NO₂, R^(k) is hydrogen; T is NR^(l),R^(l) is hydrogen; cc is 2; M is NR^(m), R^(m) is hydrogen; dd is 3; Qis NR^(n)R^(o) and R^(n) and R^(o) are each alkyl (e.g., ethyl orhydroxyethyl).

In some embodiments, R^(j) is —NO₂, R^(k) is amino (e.g., —NH₂); T isNR^(l), R^(l) is hydrogen; cc is 2; M is NR^(m), R^(m) is hydrogen; ddis 3; Q is NR^(n)R^(o) and R^(n) and R^(o) are each alkyl (e.g., ethyl).

In some embodiments, the dye is of formula XIa:

wherein

R^(j) and R^(k) are each independently hydrogen, hydroxyl, amino,alkoxy, alkyl, CN, halogen, NO₂, CF₃, SO₃H, aminocarbonyl, carbonyl,alkoxycarbonyl or an aryldiazene moiety;

cc and dd are each an integer from 1-5;

T is NR^(l) or NR^(l)CO;

M is NR^(m) or CONR^(m);

Q is NR^(n)R^(o);

R^(l), R^(m) and R^(n) are each independently hydrogen or alkyl;

R^(o) is alkyl; or R^(n) and R^(o) are linked together with the atom towhich they are attached form a 4-8 membered heterocyclic ring with 1-3heteroatoms; and cosmetically acceptable salts thereof.

In some embodiments, T is NR^(l).

In some embodiments, M is NR^(m).

In some embodiments, R^(l) and R^(m) are each hydrogen.

In some embodiments, cc is 2 and dd is 3.

In some embodiments, R^(j) is NO₂.

In some embodiments, R^(k) is hydrogen or NH₂.

In some embodiments, R^(n) and R^(o) are each alkyl (e.g., methyl, ethylor hydroxyethyl).

In some embodiments, R^(n) and R^(o) are linked to form a 6-memberedheterocyclic ring (e.g., a piperidine or morpholine ring).

In some embodiments, the dye is a compound of formula XII:

wherein

R^(p) is hydrogen or amino;

R^(q) and R^(r) are each independently hydrogen or alkyl;

ee and ff are each independently an integer from 1-5; and

R^(s) and R^(t) are each alkyl or together with the atom to which theyare attached form a 4-8 membered heterocyclic ring with 1 or 2heteroatoms, and cosmetically acceptable salts thereof.

In some embodiments, R^(p) is amino (e.g., —NH₂); R^(q) and R^(r) areeach hydrogen; ee is 2; ff is 3; and R^(s) and R^(t) are each alkyl(e.g., ethyl).

In some embodiments, R^(p), R^(q) and R^(r) are each hydrogen; ee is 2;ff is 3; and R^(s) and R^(t) are each alkyl (e.g., ethyl orhydroxyethyl).

In some embodiments, R^(r) is hydrogen.

In some embodiments, ee is 2.

In some embodiments, ff is 3.

In some embodiments, R^(s) and R^(t) are each alkyl (e.g., methyl, ethylor hydroxyethyl).

In some embodiments, R^(s) and R^(t) are linked to form a 6-memberedheterocyclic ring (e.g., piperidine or morpholine ring).

In some embodiments, R^(p) is hydrogen.

In some embodiments, R^(p) is NH₂.

In some embodiments, the dye is a compound of formula XIII:

wherein

R^(u) is hydrogen or NH₂ and

R^(v) and R^(w) are alkyl, and cosmetically acceptable salts thereof.

In some embodiments, R^(u) is hydrogen and R^(v) and R^(w) are eachethyl. In some embodiments, R^(u) is amino and R^(v) and R^(w) are eachethyl. In some embodiments, R^(u) is hydrogen, R^(v) and R^(w) aremethyl. In some embodiments, R^(u) is NH₂, R^(v) and R^(w) are methyl.In some embodiments, R^(u) is hydrogen, R^(v) and R^(w) arehydroxyethyl. In some embodiments, R^(u) is NH₂, R^(v) and R^(w) arehydroxyethyl.

In some embodiments, the dye is selected from a compound in Table 2:

TABLE 2 A

B

C

D

E

F

G

H

I

J

K

L

M

N

O

P

Q

R

S

T

U

V

W

X

Y

Z

AA

AB

AC

AD

AE

AF

AG

AH

AI

AJ

AK

AL

AM

AN

AO

AP

AQ

AR

AS

AT

AU

AV

AW

AX

or a cosmetically acceptable salt thereof.

In some embodiments, the dyes of the invention are not:

In some embodiments, the dyes of the invention are not those compoundsdisclosed in U.S. Pat. Nos. 2,750,326; 3,632,582; 3,665,036; 3,867,456;3,904,690; 4,845,293; 4,797,129; French Patent No. 2870727; NetherlandLaid Open Patent Application No. 6610759; and Great Britain PatentPublication Nos. 1150445; 1159557; 1164824 and 1164825.

The term “alkyl” includes saturated aliphatic groups, includingstraight-chain alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, etc.), branched-chain alkyl groups(isopropyl, tert-butyl, isobutyl, etc.), cycloalkyl (alicyclic) groups(cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl), alkyl substituted cycloalkyl groups, and cycloalkylsubstituted alkyl groups. The term alkyl further includes alkyl groupsthat may include oxygen, nitrogen, sulfur or phosphorous atoms replacingone or more carbons of the hydrocarbon backbone. In certain embodiments,a straight chain or branched chain alkyl has 6 or fewer carbon atoms inits backbone (e.g., C₁-C₆ for straight chain, C₃-C₆ for branched chain).Likewise, cycloalkyls may have from 3-8 carbon atoms in their ringstructure. The term “C₁-C₆” includes alkyl groups containing 1 to 6carbon atoms.

Moreover, the term alkyl includes both “unsubstituted alkyls” and“substituted alkyls,” the latter of which refers to alkyl moietieshaving substituents replacing a hydrogen on one or more carbons of thehydrocarbon backbone. Such substituents can include, for example, alkyl,alkenyl, alkynyl, halogen, hydroxyl, aryl, alkylcarbonyloxy,arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, —COOH,alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), amidino, imino, sulfhydryl, alkylthio, arylthio,thiocarboxylate, sulfates, alkylsulfinyl, sulfonate, sulfamoyl,sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl,alkylaryl, or an aromatic or heteroaromatic moiety. Cycloalkyls can befurther substituted, e.g., with the substituents described above. An“alkylaryl” or an “arylalkyl” moiety is an alkyl substituted with anaryl (e.g., phenylmethyl(benzyl)). The term “alkyl” also includes theside chains of natural and unnatural amino acids.

In one embodiment, an alkyl group may have the structure of formula VI:

R¹⁰⁴ and R¹⁰⁵ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R¹⁰⁴ and R¹⁰⁵ are absent when s is 0;

R¹⁰⁶ and R¹⁰⁷ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R¹⁰⁶ and R¹⁰⁷ are absent when t is 0;

R¹⁰⁸ and R¹⁰⁹ are each independently hydrogen, hydroxyl, alkyl, alkenyl,alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy, aryloxy,halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclic moiety orthioether, or R¹⁰⁸ and R¹⁰⁹ are absent when u is 0; or

R¹⁰⁴ and R¹⁰⁵ or R¹⁰⁵ and R¹⁰⁶ or R¹⁰⁶ and R¹⁰⁷ or R¹⁰⁷ and R¹⁰⁸ or R¹⁰⁸and R¹⁰⁹ together with the carbon atoms to which they are attached arelinked to form a 3 to 10-membered carbocyclic or heterocyclic ring;

s, t and u are integers from 0 to 5;

X is NR¹¹⁰R¹¹¹, CR¹¹²R¹¹³R¹¹⁴, OR¹¹⁵, SR¹¹⁶ or halogen;

R¹¹⁰ and R¹¹¹ are each independently hydrogen, hydroxy, alkoxy, alkyl,alkenyl, alkynyl, aryl, carbonyl, carboxy, acyl or NR¹¹⁷R¹¹⁸ or R¹⁰⁹ andR¹¹⁰ together with the nitrogen to which they are attached are linked toform a 3-10 membered aliphatic, heterocyclic or aromatic ring;

R¹¹², R¹¹³ and R¹¹⁴ are each independently hydrogen, hydroxyl, alkyl,alkenyl, alkynyl, aryl, amino, sulfonyl, carbonyl, carboxy, alkoxy,aryloxy, halogen, acyl, oximyl, hydrazinyl, —NO₂, —CN, a heterocyclicmoiety or thioether, or R¹¹² and R¹¹³ together with the carbon to whichthey are attached are linked to form a 3-10 membered carbocyclic orheterocyclic ring; or R¹¹² is absent and R¹¹³ and R¹¹⁴ together with thecarbon to which they are attached are linked to form a 4 to 10 memberedaromatic ring;

R¹¹⁵ and R¹¹⁶ are each independently hydrogen, alkyl, alkenyl, alkynyl,aryl, carbonyl, acyl or a heterocyclic moiety; and

R¹¹⁷ and R¹¹⁸ are each independently .hydrogen, alkyl, alkenyl, alkynyl,aryl, carbonyl, acyl or a heterocyclic moiety.

The term “aryl” includes groups, e.g., 5- and 6-membered single-ringaromatic groups, that may include from zero to four heteroatoms, forexample, benzene, phenyl, pyrrole, furan, thiophene, thiazole,isothiaozole, imidazole, triazole, tetrazole, pyrazole, oxazole,isooxazole, pyridine, pyrazine, pyridazine, and pyrimidine, and thelike. Furthermore, the term “aryl” includes multicyclic aryl groups,e.g., tricyclic, bicyclic, e.g., naphthalene, benzoxazole,benzodioxazole, benzothiazole, benzoimidazole, benzothiophene,methylenedioxyphenyl, quinoline, isoquinoline, napthridine, indole,benzofuran, purine, benzofuran, deazapurine, or indolizine. Those arylgroups having heteroatoms in the ring structure may also be referred toas “aryl heterocycles,” “heteroaryls” or “heteroaromatics.” The aromaticring can be substituted at one or more ring positions with suchsubstituents as described above, as for example, alkyl, alkenyl,alkynyl, halogen, hydroxyl, alkoxy, aryl, alkylcarbonyloxy,arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, —COOH,alkylcarbonyl, alkylaminoacarbonyl, arylalkyl aminocarbonyl,alkenylaminocarbonyl, alkylcarbonyl, arylcarbonyl, arylalkylcarbonyl,alkenylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), amidino, imino, sulfhydryl, alkylthio, arylthio,thiocarboxylate, sulfates, alkylsulfinyl, sulfonato, sulfamoyl,sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl,alkylaryl, or an aromatic or heteroaromatic moiety. Aryl groups can alsobe fused or bridged with alicyclic or heterocyclic rings which are notaromatic so as to form a polycycle (e.g. , tetralin). The termheteroaryl includes unsaturated cyclic compounds such as azirine,oxirene, dithiete, pyrroline, pyrrole, furan, dihydrofuran,dihydrothiophene, thiophene, pyrazole, imidazole, oxazole, thiazole,isothiazole, 12,2,3-triazole, 1,2,4, triazole, dithiazole, tetrazole,pyridine, pyran, pyrimidine, pyran, thiapyrane, diazine, thiazine,dioxine, triazine and tetrazene.

The term “heterocyclic moiety” includes saturated cyclic moieties havinga closed ring of atoms in which at least one atom is not a carbon. Asused herein, heterocyclic moieties do not include heteroaryl moieties,in which the closed ring of atoms is both heterocyclic and aromaticand/or unsaturated. Examples of heterocyclic moieties include aziridine,ethylene oxide, thiirane, dioxirane, azetidine, oxetane, thietane,dioxetane, dithietane, pyrrolidine, tetrahydrofuran,tetrahydrothiophene, imidazolidine, oxazolidine, thiazolidine,dioxolane, dithiolane, piperidine, tetrahydropyran, thiane, piperzine,pxazine, dithiane, dioxane and trioxane.

The term “heterocyclic moiety” includes both “unsubstituted heterocyclicmoieties” and “substituted heterocyclic moieties,” the latter of whichincludes moieties having substituents replacing a hydrogen on one ormore of the atoms on the closed ring. Such substituents can include, forexample, alkyl, alkenyl, alkynyl, halogens, hydroxyl, arylalkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyl oxy,aryloxycarbonyloxy, —COOH, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl,aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano,amino (including alkyl amino, dialkylamino, arylamino, diarylamino, andalkylarylamino), acylamino (including alkylcarbonylamino,arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl,alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl,sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido,heterocyclyl, alkylaryl, or an aromatic or heteroaromatic moiety.

The term “alkenyl” includes unsaturated aliphatic groups analogous inlength and possible substitution to the alkyls described above, but thatcontain at least one double bond. For example, the term “alkenyl”includes straight-chain alkenyl groups (e.g., ethylenyl, propenyl,butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, etc.),branched-chain alkenyl groups, cycloalkenyl (alicyclic) groups(cyclopropentyl, cyclobutenyl, cyclopentenyl, cyclohexenyl,cycloheptenyl, cyclooctenyl), alkyl or alkenyl substituted cycloalkenylgroups, and cycloalkyl or cycloalkenyl substituted alkenyl groups. Theterm “alkenyl” further includes alkenyl groups which include oxygen,nitrogen, sulfur or phosphorous atoms replacing one or more carbons ofthe hydrocarbon backbone. In certain embodiments, a straight chain orbranched chain alkenyl group has 6 or fewer carbon atoms in its backbone(e.g., C₂-C₆ or straight chain, C₃-C₆ for branched chain). Likewise,cycloalkenyl groups may have from 3-8 carbon atoms in their ringstructure. The term C₂-C₆ includes alkenyl groups containing 2 to 6carbon atoms.

Moreover, the term “alkenyl” includes both “unsubstituted alkenyls” and“substituted alkenyls,” the latter of which refers to alkenyl moietieshaving substituents replacing a hydrogen on one or more carbons of thehydrocarbon backbone. Such substituents can include, for example, alkyl,alkenyl, alkynyl, halogens, hydroxyl, aryl alkylcarbonyloxy,arylcarbonyloxy, alkoxycarbonyl oxy, aryloxycarbonyloxy, —COOH,alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), amidino, imino, sulfhydryl, alkylthio, arylthio,thiocarboxylate, sulfates, alkylsulfinyl, sulfonato, sulfamoyl,sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl,alkylaryl, or an aromatic or heteroaromatic moiety.

The term “alkynyl” includes unsaturated aliphatic groups analogous inlength and possible substitution to the alkyls described above, butwhich contain at least one triple bond. For example, the term “alkynyl”includes straight-chain alkynyl groups (e.g., ethynyl, propynyl,butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, etc.),branched-chain alkynyl groups, and cycloalkyl or cycloalkenylsubstituted alkynyl groups. The term “alkynyl” further includes alkynylgroups which include oxygen, nitrogen, sulfur or phosphorous atomsreplacing one or more carbons of the hydrocarbon backbone. In certainembodiments, a straight chain or branched chain alkynyl group has 6 orfewer carbon atoms in its backbone (e.g., C₂-C₆ for straight chain,C₃-C₆ for branched chain). The term C₂-C₆ includes alkynyl groupscontaining 2 to 6 carbon atoms.

Moreover, the term “alkynyl” includes both “unsubstituted alkynyls” and“substituted alkynyls,” the latter of which refers to alkynyl moietieshaving substituents replacing a hydrogen on one or more carbons of thehydrocarbon backbone. Such substituents can include, for example, alkyl,alkenyl, alkynyl, halogens, hydroxyl, aryl, alkylcarbonyloxy,arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, —COOH,alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), amidino, imino, sulfhydryl, alkylthio, arylthio,thiocarboxylate, sulfates, alkylsulfinyl, sulfonato, sulfamoyl,sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl,alkylaryl, or an aromatic or heteroaromatic moiety.

The term “acyl” includes compounds and moieties which contain the acylradical (CH₃CO—). It also includes substituted acyl moieties. The term“substituted acyl” includes acyl groups where one or more of thehydrogen atoms are replaced by for example, alkyl, alkenyl, alkynyl,halogens, hydroxyl, aryl, alkylcarbonyloxy, arylcarbonyloxy,alkoxycarbonyloxy, aryloxycarbonyloxy, —COOH, alkylcarbonyl,arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate,phosphonato, phosphinato, cyano, amino (including alkyl amino,dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino(including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido),amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,sulfates, alkylsulfinyl, sulfonato, sulfamoyl, sulfonamido, nitro,trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromaticor heteroaromatic moiety.

The term “acylamino” includes moieties wherein: an acyl moiety is bondedto an amino group. For example, the term includes alkylcarbonylamino,arylcarbonylamino, carbamoyl and ureido groups.

The terms “alkoxyalkyl,” “alkylaminoalkyl” and “thioalkoxyalkyl” includealkyl groups, as described above, which further include oxygen, nitrogenor sulfur atoms replacing one or more carbons of the hydrocarbonbackbone, e.g., oxygen, nitrogen or sulfur atoms.

The term “alkoxy” includes substituted and unsubstituted alkyl, alkenyl,and alkynyl groups covalently linked to an oxygen atom. Examples ofalkoxy groups include methoxy, ethoxy, isopropyloxy, propoxy, butoxy,and pentoxy groups.

Examples of substituted alkoxy groups include halogenated alkoxy groups.The alkoxy groups can be substituted with groups such as alkyl, alkenyl,alkynyl, halogen, hydroxyl, aryl, alkylcarbonyloxy, arylcarbonyloxy,alkoxycarbonyloxy, aryloxycarbonyloxy, —COOH, alkylcarbonyl,arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate,phosphonato, phosphinato, cyano, amino (including alkyl amino,dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino(including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido),amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,sulfates, alkylsulfinyl, sulfonato, sulfamoyl, sulfonamido, nitro,trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromaticor heteroaromatic moieties. Examples of halogen substituted alkoxygroups include, but are not limited to, fluoromethoxy, difluoromethoxy,trifluoromethoxy, chloromethoxy, dichloromethoxy, trichloromethoxy, etc.

The term “amine” or “amino” includes unsubstituted and substitutedcompounds where a nitrogen atom is covalently bonded to at least onecarbon or heteroatom including but not limited to alkyl amino, dialkylamino, aryl amino, diarylamino, and alkylarylamino. The term includes“alkyl amino” which comprises groups and compounds wherein: the nitrogenis bound to at least one additional alkyl group. The term “dialkylamino” includes groups wherein: the nitrogen atom is bound to at leasttwo additional alkyl groups. The term “arylamino”” and “diarylamino”include groups in which the nitrogen is bound to at least one or twoaryl groups, respectively. The term “alkylarylamino,” “alkylaminoaryl”or “arylaminoalkyl” refers to an amino group which is bound to at leastone alkyl group and at least one aryl group. The term “alkaminoalkyl”refers to an alkyl, alkenyl, or alkynyl group bound to a nitrogen atomwhich is also bound to an alkyl group.

The term “amide,” “amido” or “aminocarbonyl”” includes compounds ormoieties which contain a nitrogen atom which is bound to the carbon of acarbonyl or a thiocarbonyl group. The term includes “alkaminocarbonyl”or “alkylaminocarbonyl” groups which include alkyl, alkenyl, aryl oralkynyl groups bound to an amino group bound to a carbonyl group. Itincludes arylaminocarbonyl and arylcarbonylamino groups, which includearyl or heteroaryl moieties bound to an amino group that is bound to thecarbon of a carbonyl or thiocarbonyl group. The terms“alkylaminocarbonyl,” “alkenylaminocarbonyl,” “alkynylaminocarbonyl,”“arylaminocarbonyl,” “alkylcarbonylamino,” “alkenyl carbonylamino,”“alkynylcarbonylamino,” and “arylcarbonylamino” are included in term“amide.” Amides also include urea groups (aminocarbonylamino) andcarbamates (oxycarbonylamino).

The term “carbonyl” or “carboxy” includes compounds and moieties whichcontain a carbon connected with a double bond to an oxygen atom. Thecarbonyl can be further substituted with any moiety which allows thecompounds of the invention to perform its intended function. Forexample, carbonyl moieties may be substituted with alkyls, alkenyls,alkynyls, aryls, alkoxy, aminos, etc. Examples of moieties which containa carbonyl include aldehydes, ketones, carboxylic acids, amides, esters,anhydrides, etc. The term “carboxy” further includes the structure of—COOH and —COO⁻.

The term “oximyl” includes compounds and moieties that contain a carbonconnected with a double bond to a nitrogen atom, which is, in turnconnected to a hydroxyl or an alkoxyl group. The term “hydrazinyl”includes compounds and moieties that contain a carbon connected with adouble bond to a nitrogen atom, which is, in turn, connected to an aminogroup.

The term “thiocarbonyl” or “thiocarboxy” includes compounds and moietieswhich contain a carbon connected with a double bond to a sulfur atom.

The term “ether” includes compounds or moieties which contain an oxygenbonded to two different carbon atoms or heteroatoms. For example, theterm includes “alkoxyalkyl” which refers to an alkyl, alkenyl, oralkynyl group covalently bonded to an oxygen atom which is covalentlybonded to another alkyl group.

The term “thioether” includes compounds and moieties which contain asulfur atom bonded to two different carbon or hetero atoms. Examples ofthioethers include, but are not limited to, alkthioalkyls,alkthioalkenyls, and alkthioalkynyls. The term “alkthioalkyls” includecompounds with an alkyl, alkenyl, or alkynyl group bonded to a sulfuratom which is bonded to an alkyl group. Similarly, the term“alkthioalkenyls” and “alkthioalkynyl” refer to compounds or moieties inwhich an alkyl, alkenyl or alkynyl group is bonded to a sulfur atom thatis covalently bonded to an alkenyl or alkynyl group, respectively.

The term “sulfonyl” includes moieties containing a sulfonyl functionalgroup (e.g., SO₂) attached to two carbons via a covalent bond to thesulfur atom of the sulfonyl functional group.

The term “sulfonic acid” includes moieties containing a sulfonylfunctional group (e.g., SO₂) attached to one carbon and one oxygen viacovalent bonds.

The term “diazene” and “diazo” include moieties containing two nitrogenatoms covalently double bonded to each other (e.g., N═N). The nitrogenatoms may be covalently bonded to hydrogen, alkyl, alkenyl, alkynyl,hydroxyl or aryl. In some embodiments, the diazene moiety is anaryldiazene, for example, a phenyl diazene, which may be substitutedwith alkyl, alkenyl, alkynyl, halogens, hydroxyl, aryl,alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy,aryloxycarbonyloxy, —COOH, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl,aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano,amino (including alkyl amino, dialkylamino, arylamino, diarylamino, andalkylarylamino), acylamino (including alkylcarbonylamino,arylcarbonylamino, carbamoyl and ureido), amidino, imino, sulfhydryl,alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl,sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido,heterocyclyl, alkylaryl, or an aromatic or heteroaromatic moiety.

The term “hydroxy” or “hydroxyl” includes groups with an —OH or —O⁻.

The term “halogen” includes fluorine, bromine, chlorine, iodine, etc.

The term “heteroatom” includes atoms of any element other than carbon orhydrogen. Preferred heteroatoms are nitrogen, oxygen, sulfur andphosphorus.

The language “cosmetically acceptable salts” includes those salts of thedyes of the invention that acceptable for cosmetic application. One ofskill in the art would be able to readily ascertain salts that arecosmetically acceptable by referring to, for example, the InternationalCosmetic Ingredient Dictionary and Handbook, Tenth Ed., 2004 (hereinincorporated by reference in its entirety).

The dyes of the invention that are basic in nature are capable offorming a wide variety cosmetically acceptable acid addition salts ofthe dyes of the invention that are basic in nature are those that formnon-toxic acid addition salts, i.e., salts containing cosmeticallyacceptable anions, such as the hydrochloride, hydrobromide, hydroiodide,nitrate, sulfate, bisulfate, phosphate, acid phosphate, isonicotinate,acetate, lactate, salicylate, citrate, acid citrate, tartrate,pantothenate, bitartrate, ascorbate, succinate, maleate, gentisinate,fumarate, gluconate, glucaronate, saccharate, formate, benzoate,glutamate, methanesulfonate, ethanesulfonate, benzenesulfonate,p-toluenesulfonate and palmoate (i.e.,1,1′-methylene-bis-(2-hydroxy-3-naphthoate)]salts. The acid additionsalts of the base dyes are readily prepared by treating the basecompound with a substantially equivalent amount of the chosen mineral ororganic acid in an aqueous solvent medium or in a suitable organicsolvent, such as methanol or ethanol. Upon careful evaporation of thesolvent, the desired solid salt is readily obtained. The preparation ofother dyes of the invention not specifically described in theexperimental section can be accomplished using combinations of thedescribed reactions that will be apparent to those skilled in the art.

The dyes of the invention that are acidic in nature are capable offorming a wide variety of base salts. The chemical bases that may beused as reagents to prepare cosmetically acceptable base salts of thedyes of the invention that are acidic in nature are those that formnon-toxic base salts with such compounds. Such non-toxic base saltsinclude, but are not limited to those derived from such cosmeticallyacceptable cations such as alkali metal cations (e.g., potassium andsodium) and alkaline earth metal cations (e.g., calcium and magnesium),ammonium or water-soluble amine addition salts such asN-methylglucamine-(meglumine), and the lower alkanolammoniums and otherbase salts of cosmetically acceptable organic amines. The cosmeticallyacceptable base addition salts of the dyes of the invention that areacidic in nature may be formed with cosmetically acceptable cations byconventional methods. Thus, these salts may be readily prepared bytreating the dyes of the invention with an aqueous solution of thedesired cosmetically acceptable cation and evaporating the resultingsolution to dryness, preferably under reduced pressure. Alternatively, alower alkyl alcohol solution of the dyes of the invention may be mixedwith an alkoxide of the desired metal and the solution subsequentlyevaporated to dryness.

II. Dye Compositions

In some aspects, the present invention provides dye compositioncontaining at least one dye of the invention and a medium suitable fordyeing keratin fibers (e.g., hair). The language “medium suitable fordyeing keratin fibers” includes mediums that are capable of containingat least one dye of the invention and include, for example, solutions,sprays, rinses, mousses, gels, powders, shampoos and creams.

In some embodiments, the dye compositions contain one or more directdyes or oxidative dyes in addition to containing at least one dye of theinvention. Where the dye composition contains one or more oxidativedyes, the dye or dyes of the invention in the composition may act as aspectator dye. The language “specatator dye” includes the dye of theinvention being present in the dye solution or composition but notparticipating in the oxidative reaction required by the oxidative dyesto provide color.

In other embodiments, the dyes of the invention are formulated as acolor booster. The language “color booster” includes dye compositionscomprising at least one dye of the invention that may be added to a dyecomposition containing one or more direct dyes or oxidative dyes inorder to enhance the color and/or increase the vibrancy of the dyecomposition after application to hair. In some embodiments, the colorbooster may be applied to the hair in the same composition as the dyecomposition containing one or more direct or oxidative dyes. In otherembodiments, the color booster may be applied to the hair in a separatecomposition from that of the composition containing one or more director oxidative dyes, and may be added prior to, at substantially the sametime, or after application of the composition containing one or moredirect or oxidative dyes.

In other embodiments, the medium is an aqueous medium. The language“aqueous medium” includes a medium that contains about 5%, about 10%,about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%,about 80%, about 85%, about 90% or about 95% water.

In still other embodiments, the medium further includes one or more ofsurfactants, thickeners, fragrances, sequestering agents, UV-screeningagents, waxes, silicones, preserving agents, ceramides, oils, vitamins,provitamins, opacifiers, couplers, primary intermediates, alkalizingagents, direct dyes, reducing agents, antioxidants, emulsifiers,chelating agents, color retarders, solvents and buffers (e.g., phosphatebuffers). Examples of the foregoing agents may be found in theInternational Cosmetic Ingredient Dictionary and Handbook, Tenth Ed.,2004 (herein incorporated by reference in its entirety).

Examples of surfactants include, but are not limited to, oleth 5, oleicacid and sodium lauryl sulfate.

Examples of thickeners include, but are not limited to, fatty alcohols(e.g., oleyl alcohol), ethoxylated phenols (e.g., octoxynol-1,nonoxynol-4, and nonoxynol-9), and polymers (e.g.,hydroxyethylcellulose).

Examples of couplers include, but are not limited to, 3-aminophenol,resorcinol, 2-methylresorcinol, 1-naphthol, 2-methyl-5-aminophenol, and4-amino-2-hydroxytoluene.

An examples of a primary intermediate includes but are not limited to,parapheynylenediamine and 4-aminophenol.

Examples of antioxidants include, but are not limited to, sodium sulfiteand erythorbic acid.

Examples of emulsifiers include, but are not limited to, Pluracare L64®and Inconam 30®.

An example of a chelating agent includes, but is not limited to, EDTA.

Examples of solvents include, but are not limited to, water, C₁ to C₄lower alcohols (e.g., ethanol, 2-propanol and isopropanol), acetone,methylethylcetone, ethyl acetate, methyl acetate, butyl acetate,diethoxyethane, dimethoxyethane, C₆ to C₁₀ alkanes, dimethyl isosorbide,ethoxydiglycol and propylene glycol.

Examples of alkalizing agents include, ammonium hydroxide, ammonia,alkylamines (e.g., ethylamine; dipropylamine; triethylamine;n-propylamine, isobutylamine, 2-ethylbutylamine, diethylamine),alkanediamines (e.g., 1,3-diaminopropane; ethylenediamine;1,2-diaminopropane; diethylenetriamine; triethylenetriamine;2,2′-iminodipropylamine; 3,3-iminodipropylamine; andbis-hexamethylenetriamine), alkanolamines (e.g., ethanolamine,diethanolamine, isopropanolamine; di-isopropanolamine; triethanolamine;triisopropanolamine; N-methyldiethanolamine; diisopropylethanolamine;dimethylisopropanolamine; 2-amino-2-methylpropane-1,3-diol;tris(hydroxymethyl)methylamine; N-(2-hydroxyethyl)aniline;N-methyl-N(2-hydroxyethyl)aniline; N,N-bis(2-hydroxyethyl)aniline),polyalkylenepolyamines, (e.g., diethylenetriamine), heterocyclic amines(e.g., morpholine; N-methylmorpholine, N-ethylmorpholine,N-hydroxyethylmorpholine, N-phenylmorpholine, piperidine,N-hydroxyethylpiperidine, and piperazine), alkaline earth hydroxides(e.g., calcium hydroxide or magnesium hydroxide) alkali metal hydroxide(e.g., sodium hydroxide or potassium hydroxide), or carbonates (e.g.,sodium carbonate and bicarbonate).

In particular embodiments, the alkalizing agent is present in thecomposition between about 0.05% to about 10%, between about 0.1% andabout 5% or between about 1.5% to about 3.5%.

In some embodiments, the dye composition is formulated in a cosmeticallyacceptable composition. The language “cosmetically acceptablecomposition” includes dye compositions that comprise at least one dye ofthe invention and are suitable for cosmetic application. One of skill inthe art would be able to readily ascertain formulations and compositionsthat are cosmetically acceptable by referring to, for example, theInternational Cosmetic Ingredient Dictionary and Handbook, Tenth Ed.,2004 (herein incorporated by reference in its entirety).

In some embodiments, the dye composition comprises about 3% dye of theinvention, about 15% of an emulsifier (e.g., Pluracare L64® or Incronam30®), about 25% of a solvent (e.g., dimethyl isosorbide) and about 53%aqueous phosphate buffer.

In other embodiments, the dye composition composition comprises about0.1% to 3% dye of the invention, about 50% solvent (e.g., ethanol) andthe remaining solution of a phosphate buffer.

In still other embodiments, the dye composition comprises about 0.1-3%dye of the invention, between about 1.5% to about 3.5% ammonia, about0.05% stabilizer (e.g., EDTA), about 0.4% antioxidant (e.g., sodiumsulfite and/or isoascorbic acid), between about 20% and about 25% ofsolvent (e.g., ethoxydiglycol) and about 30% surfactant (e.g., oleth-5and/or oleic acid) with the remaining solution comprising water.

In still other embodiments, the dye composition comprises about 0.1-3%dye of the invention, between about 1.5% to about 3.5% ammonia, about0.05% stabilizer (e.g., EDTA), about 0.2% antioxidant (e.g., sodiumsulfite), between about 8% and about 25% solvent (e.g., propylene glycoland/or 2-propanol), about 2% surfactant (e.g., sodium lauryl sulfate),about 21% buffer (e.g., oleic acid), about 10% thickener (e.g., oleylalcohol) with the remaining solution comprising water.

In some embodiments, the dyes of the invention are formulated in anafter-coloring conditioner (e.g., L'Oreal Superior Preference CareSuprême Color-Saving Conditioner) and similar formulations forapplication during conditioning.

III. Methods

In some aspects, the present invention provides methods for coloringkeratin fibers by applying to the keratin fibers a dye compositioncomprising at least one dye of the invention. The term “keratin fibers”includes human hair and animal fur.

In some aspects, the present invention provides methods for coloringsynthetic hair by applying to the synthetic hair a dye compositioncomprising at least one dye of the invention. The term “synthetic hair”includes hair or fur made from non-natural fibers, for example, fake or“faux” fur and synthetic hair wigs.

In some aspects, the present invention provides methods for coloringhair by applying to hair a dye composition comprising at least one dyeof the invention. The language “coloring hair” includes treatingsubstantially all of the hair on a person's head or some of the hair ona person's head

In some aspects, the present invention provides methods for coloringdamaged hair by applying to hair a dye composition comprising at leastone dye of the invention. The language “coloring damaged hair” includestreating all of the hair on a person's head or someof the hair on aperson's head, where the hair is more porous than normal hair.

In some aspects, the present invention provides methods for highlightinghair by applying to hair a dye composition comprising at least one dyeof the invention. The language “highlighting hair” includes treatingsome of the hair on a person's head.

In other aspects, the present invention provides methods for touching uphair roots by applying to the roots a dye composition comprising atleast one dye of the invention. The language “touching up hair roots”includes treating the hair on a person's head that is closest to thescalp.

In some embodiments, the dye composition comprising at least one dye ofthe invention is applied to wet or dry hair.

In other embodiments, the methods include the step of leaving thecomposition comprising at least one dye of the invention on the hair forbetween about 1 and 60 minutes.

In some other embodiments, the methods include the steps of a) treatingthe hair with an oxidative dye in the presence of ammonia and optionallyhydrogen peroxide for between about 1 and about 60 minutes; b)optionally rinsing the hair; and optionally partially drying the hair;c) treating the hair with a dye composition comprising at least one dyeof of the invention for between about 1 and about 60 minutes; and d)rinsing the hair. The methods may also include the steps of e) washingthe hair with shampoo and/or conditioning the hair with conditionerafter rinsing the hair; f) rinsing the hair; and g) optionally dryingthe hair.

In some embodiments, the methods further comprises the steps of a)treating the hair with a dye composition comprising at least one dye ofthe invention optionally containing one or more oxidative dye precursorsand/or one or more direct dyes with one or more alkalizing agents and,optionally, hydrogen peroxide for between about 1 and about 60 minutes;b) rinsing the hair; c) washing the hair with shampoo and/orconditioning the hair with conditioner; d) rinsing the hair; and e)optionally drying the hair.

IV. Kits

In some aspects, the present invention provides for kits comprising adye composition comprising at least one dye of the inventioninstructions for use. In some embodiments, the dye is formulated as acosmetically acceptable formulation. In some embodiments, thecosmetically acceptable formulation may further comprise ammonia.

In other embodiments, the kit may contain, for example, a developerbottle, gloves or a conditioning rinse. In some other embodiments, thedeveloper bottle contain may contain a solution comprising hydrogenperoxide. In yet other embodiments, one or more dyes of the inventionare packaged separately from the dye composition.

Exemplification of the Invention

The methods of this invention can be understood further by the followingexamples. It will be appreciated, however, that these examples do notlimit the invention. Variations of the invention, now known or furtherdeveloped, are considered to fall within the scope of the presentinvention as described herein and as hereinafter claimed.

EXAMPLE 1 Synthesis of Selected Dyes of the Inventions

Synthesis of Compounds A-F: The synthesis of compounds A-F weresynthesized as shown below in Scheme 1.

N-Ethylaniline (1, 50.00 g, 0.412 mol) was added to a stirred solutionof NaH (1.2 eq, 11.86 g, 0.495 mol) in THF (300 mL) at 0° C. followed byethyl bromoacetate (2, 1.2 eq, 82.69 g, 0.495 mol). The reaction mixturewas warmed to room temperature and continued stirring for 30 minutes.The reaction mixture temperature was increased to 55° C. and stirred for14 hours. The reaction mixture was brought to room temperature, quenchedwith ice-water and extracted with EtOAc (3×300 mL). The resultantextracted EtOAc was washed with water (2×300 ml), dried over Na₂SO₄, andconcentrated. The concentrated product was purified through columnchromatography using 5% EtOAc in petroleum ether to afford compound 3 asbrown liquid (80 g, 93.5%). Rf: 0.8 (petroleum ether: EtOAc, 9:1). ¹HNMR (300 MHz, CDC1₃): δ 7.27-7.20 (m, 2H), 6.75-6.65 (m, 3H), 4.21 (q,J=7.1 Hz, 2H), 4.02 (s, 2H), 3.99 (q, J=7.1 Hz, 2H), 1.27 (t, J=7.1 Hz,3H), 1.22 (t, J=7.1 Hz, 3H). LCMS, single peak, 4.188 min, ES-APCI: m/z208.2 [M+H]+.

To a stirred solution of 2-chloro-4-nitroaniline (4, 1.5 eq, 50.00 g,0.289 mol) in acetonitrile (715 mL) and 1N HCl (1.285 L) was addeddropwise NaNO₂ (1.5 eq, 20.00 g, 0.289 mol) in water (150 mL) at 0° C.over a period of 30 minutes and continued stirring for 1.5 hour. Theresultant reaction mixture was added to 3 (1.0 eq, 38.25 g, 0.185 mol)with sulfamic acid (0.1 eq, 1.80 g, 18.5 mmol) in acetonitrile (1.150 L)and 1 M HCl (1.150 L) at 0° C. over a period of 45 minutes withcontinued stirring for 60 minutes. Saturated sodium bicarbonate was thenadded to the resultant reaction mixture at 0° C. to adjust to a pH ofabout 1 and the mixture was stirred for 1.2 hours at the sametemperature. Next, the reaction mixture was extracted withdichloromethane (4×1 L),dried over Na₂SO₄, and concentrated. Theconcentrated product was stirred with methyl t-butyl ether (500 ml) for30 minutes and filtered to afford 5 as dark red solid (35 g, 48.5%). Rf:0.6(pet. ether: EtOAc, 9:1). ¹H NMR (400 MHz, DMSO-d6): δ 8.46 (bs, 1H),8.28-8.25 (m, 1H), 7.88 (d, J=9.0 Hz, 2H), 7.79 (d, J=8.9 Hz, 1H), 6.84(d, J=9.0 Hz, 2H), 4.38 (s, 2H), 4.16 (q, J=7.1 Hz, 2H), 3.58 (q, J=7.1Hz, 2H), 1.22 (t, J=7.1 Hz, 3H), 1.82 (t, J=7.1 Hz, 3H). LCMS, singlepeak, 4.965 min, ES-APCI: m/z 390.9 [M+H]+.

Lithium hydroxide (2.6 eq, 3.23 g, 0.135 mol) in H₂O (20 mL) was addedto a stirred solution of 5 (1.0 eq, 20.00 g, 0.051 mol) intetrahydrofuran (120 mL) and water (120 mL) at 0° C., which was allowedto stir at room temperature for 1.5 hours. The tetrahydrofuran wasevaporated under vacuum and the pH adjusted to approximately 7 using acitric acid solution. The resultant reaction mixture was extracted withethyl acetate (2×200 mL). The organic layer was dried over Na₂SO₄ andconcentrated. The concentrated product was triturated with 100 mLEt₂O-EtOAc (8:2) to afford 6 as a dark pink solid (14 g, 75.4%). Rf 0.2(CHCl₃:MeOH, 9:1). ¹H NMR (300 MHz, CDCl₃): δ 8.35 (s, 1H), 8.12 (d,J=9.0 Hz, 1H), 7.90 (d, J=9.3 Hz), 7.73 (d, J=9.0 Hz, 1H), 6.70 (d,J=9.3 Hz, 2H), 4.10 (s, 2H), 3.55 (q, J=7.1 Hz, 2H), 1.26 (t, J=7.2 Hz,3H). LCMS, single peak, 4.729 min, ES-APCI: m/z 362.9 [M+H]+. HPLCpurity: 97.6%.

Compound A: N-(3-aminopropyl)diethanolamine (1 eq, 298 mg, 1.84 mmol,CAS #4985-85-7) was dissolved in 10 mL of 9:1 CH₂Cl₂:DMF. An amount of1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC, 2.0eq, 571 mg, 3.68 mmol), 1-hydroxybenzotriazole hydrate (HOBt, 1.5 eq,422 mg, 2.76 mmol), and N,N-diisopropylethylamine (DIPEA, 2.0 eq, 640μL, 3.68 mmol) were added to a stiffing solution of amine. Compound 6(1.2 eq, 1.00 g, 2.76 mmol) was dissolved in 5 mL of 9:1 CH₂Cl₂:DMF andadded to the reaction vessel. The mixture was stirred at roomtemperature overnight and was subsequently diluted with 30 mL of CH₂Cl₂and washed with saturated sodium bicarbonate (2×30 mL) and brine(1×30mL), dried over Na₂SO₄ and concentrated by rotary evaporation.After column chromatography (2×), the yield was 47%. ¹H NMR (300 MHz,CDCl₃): δ 8.25 (s, 1H), 8.04 (d, J=9.0 Hz, 1H), 7.85 (d, J=9.0 Hz, 2H),7.67 (d, J=9.0 Hz, 1H), 6.89 (bt, J=5.9 Hz, 1H, NH), 6.72 (d, J=9.0 Hz,2H), 3.98 (s, 2H), 3.54 (m, 6H), 3.40 (q, J=6.7 Hz, 2H), 2.53 (t, J=5.0Hz, 4H), 2.46 (t, J=6.2 Hz, 2H), 1.65 (quintet, J=6.3 Hz, 2H), 1.27 (t,J=6.7 Hz, 3H). LCMS, single peak, 2.554 min, ES-APCI: m/z 507.2 [M+H]+.

Compound B: Using a similar procedure as outlined for compound A, anamount of 6 (1.2 eq, 435 mg, 1.20 mmol) was reacted with and3-(diethylamino)polyamine (1.0 eq, 130 mg, 158 μL, 1.00 mmol,CAS#104-78-9). In addition to the washes, the organic fractions weretaken up in CH₂Cl₂ and loaded onto a Thermo Scientific 5 g HyperSep SCXcartridge. The cartridge was washed with 25 mL each of CH₂Cl₂ then MeOHand was then eluted with 2 M NH₃ in MeOH to yield a dark red/purplesolid. Yield: 78%. ¹H NMR (300 MHz, CDCl₃): δ 8.40 (s, 1H), 8.16 (d,J=9.0 Hz, 1H), 7.95 (d, J=9.0 Hz, 2H), 7.78 (d, J=9.0 Hz, 1H), 7.67 (bt,1H, NH), 6.77 (d, J=9.0 Hz, 2H), 3.99 (s, 2H), 3.57 (q, J=7.1 Hz, 2H),3.38 (q, J=6.1 Hz, 2H), 2.41 (t, J=6.1 Hz, 2H), 2.34 (q, J=7.1 Hz, 4H),1.59 (quintet, J=6.1 Hz, 2H), 1.27 (t, J=7.1 Hz, 3H), 0.84 (t, J=7.1 Hz,6H). LCMS, single peak, 3.257 min, ES-APCI: m/z 475.2 [M+H]+.

Compound C: Compound C was synthesized in a similar manner as compoundA, above. Starting with compound 6 (1.2 eq, 268 mg, 0.739 mmol) andreacting with N-(3-aminopropyl)morpholine (1.0 eq, 88.8 mg, 89.7 μL,0.616 mmol, CAS#123-00-2) yielded a dark red/purple residue. Yield: 90%.¹H NMR (400 MHz, CDCl₃): δ 8.41 (d, 1H, J=2.4 Hz), 8.17 (dd, 1H, J=2.4Hz, and 8.9 Hz), 7.97 (d, 2H, J=9.1 Hz), 7.78 (d, 1H, J=8.9 Hz), 7.0(brs, 1H), 6.81 (d, 2H, J=9.1Hz), 4.01 (s, 2H), 3.62-3.59 (m, 6H), 3.38(q, 2H, J=6.3 Hz), 2.36 (brs, 6H), 1.70 (t, 2H, J=6.4 Hz), 1.30 (t, 3H,J=7.0 Hz). LCMS, single peak, 3.935 min, ES-APCI: m/z 489.2 [M+H]+.

Synthesis of Compounds G and J: Compounds G and J were synthesized asshown in Scheme 2.

Compound 9 was either purchased from Polymer Source, Inc. or synthesizedas follows: Disperse red 13 dye (8, 13.14 g, 37.68 mmol, 1.0 eq) wasdissolved in 250 mL of tetrahydrofuran (THF) and triethylamine (NEt₃,33.62 mL, 241 mmol, 6.4 eq), and the mixture was cooled in an ice bath.Acryloyl chloride (5.70 g, 5.36 mL, 65.95 mmol, 1.75 eq) was added in 55mL of THF dropwise with an addition funnel to the reaction mixture withstiffing. The mixture was then allowed to warm to room temperature andwas stirred overnight. Excess acryloyl chloride was quenched with theaddition of 200 mL of saturated sodium bicarbonate, and the product wasextracted with 1×200 mL and 2×100 mL of CHCl₃. The organic portion wasdried over Na₂SO₄ and concentrated by rotary evaporation to yield a darkred/purple residue. Co-evaporation with a 125 mL of a 3:2 mixture ofacetone and MeOH led to the isolation of a dark purple solid (9). Yield:96%. ¹H NMR (CDCl₃, 300 MHz, 25° C.): δ 8.38 (s, 1H),8.14 (d, J=9.0 Hz,1H), 7.94 (d, J=9.2 Hz, 2H), 7.77 (d, J=9.0 Hz, 1H), 6.81 (d, J=9.2 Hz,2H), 6.42 (d, J=17.5 Hz, 1H), 6.12 (dd, J=17.5, 10.4 Hz, 1H), 5.87 (d,J=10.4 Hz, 1H), 4.36 (t, J=6.2 Hz, 2H), 3.74 (t, J=6.2 Hz, 2H), 3.54 (q,J=7.1 Hz, 2H), 1.27 (t, J=7.1 Hz, 3H).

Compound J: Ethylene diamine (323 mg, 360 μL, 5.37 mmol, 1.0 eq) wasdissolved in 10 mL of CHCl₃ and cooled on ice. Compound 9 (2.16 g, 5.37mmol) was dissolved in 15 mL of CHCl₃ and added dropwise via syringe tothe stiffing, cooled mixture. The mixture was stirred at 50-60° C. for 2days. ¹H NMR (CDCl₃, 400 MHz, 25° C.): δ 8.37 (s, 1H), 8.14 (d, J=9.0Hz, 1H), 7.92 (d, 2H), 7.77 (d, J=9.0 Hz, 1H), 6.79 (d, 2H), 4.31 (m,2H), 3.69 (t, 2H), 3.53 (t, 2H), 2.87 (m, 2H), 2.75 (m, 2H), 2.65 (m,2H), 2.51 (m, 2H), 1.26 (t, 3H).

Synthesis of Compounds U-AA: Compounds U-AA were synthesized as shown inScheme 3.

Compounds U-AA were prepared by dissolving compound 9 in CHCl₃ andadding compound 9 dropwise to 0.5 eq of amine dissolved in CHCl₃ andcooled on ice. The mixture was stirred at 50-60° C. for 2 days.

Synthesis of Compounds AB-AH: Compounds AB-AH were synthesized as shownin Scheme 4.

Using a similar procedure as outlined immediately above, compounds AB-AHwere synthesized. Compound 13 is synthesized as follows: Compound 12(1.0 eq) is dissolved in 250 mL of tetrahydrofuran (THF) andtriethylamine (NEt₃, 6.4 eq), and the mixture is cooled in an ice bath.Acryloyl chloride (1.75 eq) is added in 55 mL of THF dropwise with anaddition funnel to the reaction mixture with stirring. The mixture isthen allowed to warm to room and is stirred overnight. Excess acryloylchloride is quenched with the addition of 200 mL of saturated sodiumbicarbonate, and the product is extracted with 1×200 mL and 2×100 mL ofCHCl₃. The organic portion is dried over Na₂SO₄ and concentrated byrotary evaporation. Co-evaporation with a 125 mL of a 3:2 mixture ofacetone and MeOH leads to the isolation of compound 13.

Synthesis of Compounds AI and AJ: Compounds AI and AJ were synthesizedas shown in Scheme 5.

Compound 8 (5.00 g, 14.34 mmol) was added to a stirred solution ofepichlorohydrin (2.0 eq, 2.65 g, 28.65 mmol) in 50% aq. sodium hydroxide(25 g of NaOH in 50 ml of H₂O) and THF (10 ml) followed by addition oftetrabutylammoniumhydrogen sulfate (0.1 eq, 470 mg, 1.41 mmol) at roomtemperature. The resultant reaction mixture was stirred vigorously usinga mechanical stirrer for 16 hours at room temperature. After completionof the reaction, water (20 ml) was added to reaction mixture, and theproduct was extracted with dichloromethane (2×200 ml). The extracteddichloromethane was dried over Na₂SO₄ and concentrated by rotaryevaporation. The resulting concentrated product was purified throughcolumn chromatography using 80% dichloromethane in pet ether to affordpure product 15 as a dark purple/black viscous liquid (3.5 g, 60%). Rf0.4 (pet ether:ethyl acetate, 7:3). ¹H NMR (400 MHz, CDCl₃): δ 8.41 (s,1H), 8.16 (d, J=8.9 Hz, 1H), 7.96-7.93 (d, J=9.2 Hz, 2H), 7.79 (d, J=8.9Hz, 1H), 6.79 (d, J=9.2 Hz, 2H), 3.74-3.71 (m, 1H), 3.80-3.72 (m, 2H),3.68-3.62 (m, 2H), 3.58 (q, J=7.1 Hz, 2H), 3.39 (dd, J=11.6, 6.0 Hz,2H), 3.18-3.14 (m, 1H), 2.83-2.81(m, 1H), 2.63-2.61 (m, 1H), 1.27 (t,J=7.1 Hz, 3H). ¹³C NMR (100 MHz, CDCl₃): δ 153.2, 152.0, 147.0, 144.2,133.9, 127.1, 126.1, 122.7, 118.0, 111.5, 72.1, 69.0, 50.9, 50.4, 46.2,44.1, 12.3. LCMS, single peak, 4.130 min, ES-APCI: m/z 404.9 [M+H]+.

Compound AJ: Epoxide 15 (1.00 g, 2.47 mmol) was dissolved in 900 μL ofDMF. Neat (±)-3-amino-1,2-propanediol (0.5 eq, 113 mg, 1.24 mmol) wasadded to the stirring reaction mixture. The mixture was stirred at 95°C. overnight. The mixture was diluted into 20 mL of EtOAc and washedsaturated sodium bicarbonate (2×15 mL) and brine (1×10 mL), dried overNa₂SO₄ and concentrated by rotary evaporation to yield a dark red purpleresidue. The yield was quantitative. ¹H NMR (400 MHz, CDCl₃): δ 8.37 (s,2H), 8.15 (d, J=8.9 Hz, 2H), 7.92 (d, J=9.2 Hz, 4H), 7.78 (d, J=8.9 Hz,2H), 6.77 (d, J=9.2 Hz, 4H), 3.83 (m, 2H), 3.67 (m, 4H), 3.63 (m, 5H),3.53 (m, 5H), 3.45 (m, 3H), 3.38 (m, 2H), 2.65 (m, 1H), 2.60 (m, 4H),2.44 (m, 1H), 1.62 (s, 3H, —OH), 1.23 (t, J=7.1 Hz, 6H).

Synthesis of Compounds AK and AL: Compounds AK and AL were synthesizedas shown in Scheme 6.

2-Chloroethylamine hydrochloride (14.32 g, 123.5 mmol, 3.3 eq) wasdissolved in 100 mL of chloroform and N,N-diisopropylethylamine (DIPEA,32.59 mL, 24.18 g, 187.1 mmol, 5.0 eq). 1-Fluoro-2-nitrobenzene (17,5.28 g, 3.97 mL, 37.42 mmol, 1.0 eq) was slowly added to the stiffingmixture at room temperature. The mixture was then heated to reflux undera condenser for 2 days. The reaction mixture was diluted with 100 mL ofwater, and the product was extracted with 1×50 mL and 1×25 mL of CHCl₃.The organic portion was washed with 1×100 mL and 1×50 mL of brine, driedover Na₂SO₄, and concentrated by rotary evaporation to yield the product18 as an orange residue. Yield: 22%. ¹H NMR (CDCl₃, 400 MHz, 25° C.): δ8.25 (s, 1H, NH), 8.19 (dd, J=8.6, 1.5 Hz, 1H), 7.50-7.43 (m, 1H), 6.86(d, J=8.6 Hz, 1H), 6.70 (ddd, J=10.6, 5.9, 2.4 Hz, 1H), 3.80-3.74 (m,2H), 3.74-3.67 (m, 2H).

Compound AK: Compound 18 (1.26 g, 6.28 mmol) was dissolved in 15 mL ofCHCl₃ and DIPEA (5.47 mL, 4.06 g, 31.40 mmol, 5.0 eq).N-(3-aminopropyl)diethanolamine (3.06 g, 3.70 mL, 18.84 mmol, 3.0 eq)was dissolved in 10 mL of CHCl₃ and was added to the stiffing reactionmixture along with approximately 5 mL of CHCl₃ rinse. The mixture washeated to reflux for 2 days. The product was purified through columnchromatography eluting with 0.5% triethylamine and 4% methanol inchloroform. Yield: 23%. ¹H NMR (CDCl₃, 400 MHz, 25° C.): δ 8.15 (bs, 1H,NH), 8.12 (dd, J=8.6, 1.6 Hz, 1H), 7.41 (ddd, J=8.5, 7.0, 1.2 Hz, 1H),6.85 (dd, J=6.7, 1.9 Hz, 1H), 6.61 (ddd, J=8.4, 5.6, 1.2 Hz, 1H), 3.63(dd, J=6.8, 3.7 Hz, 4H), 3.45 (s, 1H, NH), 3.38 (dd, J=12.1, 6.7 Hz,2H), 3.10-2.46 (m, 10H), 1.88 (p, J=6.8 Hz, 2H).

Synthesis of Compound AN: Compound AN was synthesized as shown in Scheme7.

Compound AN: 4-Fluoro-2-nitroaniline (20, 1.08 g, 6.91 mmol) wasdissolved in 8 mL of methanol and DIPEA (4.61 mL, 3.42 g, 26.48 mmol,3.8 eq). N³-(2-aminoethyl)-N¹,N¹-diethyl-1,3-propanediamine (1.73 g,10.00 mmol, 1.4 eq) was dissolved in 5 mL of methanol and was added tothe stiffing reaction mixture along with approximately 5 mL of methanolrinse. The mixture was heated to reflux for 2 days. The product waspurified through column chromatography eluting with 1% triethylamine and4% methanol in chloroform. Yield: 3.8%. ¹H NMR (400 MHz, MeOD) δ 7.50(d, J=2.7 Hz, 1H), 7.09 (dd, J=9.1, 2.8 Hz, 1H), 6.92 (d, J=9.1 Hz, 1H),3.45 (t, J=6.3 Hz, 2H), 2.87 (t, J=6.3 Hz, 2H), 2.65 (t, J=7.0 Hz, 2H),2.63-2.49 (m, 6H), 1.76-1.63 (m, 2H), 1.11-0.99 (t, J=7.2 Hz, 6H).

EXAMPLE 2 Exemplary Formulations

The formulations set forth below were prepared for testing certain dyesof the invention. One of skill in the art would be able to determine theappropriate amounts or ranges of the formulation components with no morethan routine experimentation.

Formulation 1

Ingredients % w/w Phosphate Buffer w/DI water q.s. Dimethyl Isosorbide(Solvent) 25% Pluracare L64 (Emulsifier) 15% Compound G (Dye)  3%

Formulation 2

Ingredients % w/w Phosphate Buffer w/DI water q.s. Dimethyl Isosorbide(Solvent) 24% Incronam 30 (Emulsifier) 15% Compound U (Dye)  3%

Formulation 3

Ingredients % w/w Phosphate Buffer w/DI water q.s. Ethanol (Solvent)  50% Compound AC (Dye) 0.1-3%

Formulation 4

Ingredients % w/w Water q.s. EDTA (stabilizer) 0.05%  Sodium sulfite(antioxidant) 0.2% Isoascorbic acid (aka erythorbic acid, antioxidant)0.2% Ethoxydiglycol (aka transcutol, solvent) 20-25%  Oleth-5 (tradenameVolpo 5, surfactant)  10% Oleic acid (surfactant/buffer)  20% Ammonia1.68-3.36%      Compound B (Dye) 0.1-3% 

Formulation 5

Ingredients % w/w Water q.s. EDTA (stabilizer) 0.05%  Sodium sulfite(antioxidant) 0.2%  Propylene glycol (solvent) 3-5%  2-propanol(solvent) 5-20%  Sodium lauryl sulfate (surfactant)  2% Oleic acid(surfactant/buffer) 21% Oleyl alcohol (tradename Lipocol O/95,thickener) 10% Ammonia 1.68-3.36%     Compound B (Dye) 0.1-3%  

Formulation 6

Ingredients % w/w Water q.s. EDTA (stabilizer) 0.2% Sodium sulfite(antioxidant) 1.0% Ethoxydiglycol (tradename Transcutol CG, solvent)5-10%  Paraphenylenediamine (PPD, primary intermediate) 0.3%3-Aminophenol (MAP, coupler) 0.06%  Resorcinol (coupler) 0.24%  Cetylalcohol (tradename Lanette 16, fatty alcohol)  2% Emulium Delta (fattyalcohol blend)  8% Neopentyl glycol diheptanate (tradename Lexfeel 7) 5% Aminomethylpropylamine (AMP, base) 0.2-1%  Compound AK (Dye) 0.1-3% 

Formulation 7

Ingredients % w/w Water q.s. EDTA (stabilizer) 0.05% Sodium sulfite(antioxidant)  0.1% Erythorbic acid (antioxidant)  0.4% Ethoxydiglycol(tradename Transcutol CG, solvent) 5-10% Paraphenylenediamine (PPD,primary intermediate) 0.21% 4-Aminophenol (PAP, primary intermediate)0.37% Resorcinol (coupler) 0.08% 2-Methylresorcinol (coupler) 0.39%1-Naphthol (coupler) 0.02% 4-Amino-2-hydroxytoluene (AHT, coupler) 0.06%Oleth-5 (tradename Brij ™ O5-LQ-(MH), surfactant) 10-15%  Oleic acid(surfactant/buffer)  20% Ammonia (base) 1.68-3.36%    Compound AK (Dye)0.1-3% 

EXAMPLE 3 Colorimetry Evaluation of Exemplary Dyes of the Invention

Materials: Virgin light blond, virgin light brown, virgin medium brown,and single bleached medium brown hair were purchased from InternationalHair Importers (Glendale, N.Y.). BW 2000 Ultra Concentrated bleachingpowder, 20V Hydrogen Peroxide Pure White, and 40V Hydrogen Peroxide PureWhite were purchased from Clairol Professional (Stamford, Conn.).Shampoo was a solution of 7.5% (w/w) sodium lauryl sulfate (SLS,Spectrum Chemical, Gardena, Calif.) in deionized water.

Bleaching: An amount of 1 gram of virgin hair tresses from InternationalHair Importers was used, which had enough thickness that when laid flaton a surface the background was not seen. The bleach paste was freshlymade prior to use by mixing 5.57 gram per tress of the BW 2000 UltraConcentrated bleaching powder with 10 mL per tress of Pure White 20 Vhydrogen peroxide solution. The thick, lumpy white paste was spreadquickly over both sides of the hair tresses, and then, the timer wasstarted. The paste was then spread uniformly with the fingers (gloves)into the tress so that the latter was well saturated. The tress waswrapped in aluminum foil and left to stand for a total of 30 minutes atroom temperature after which the tress was thoroughly rinsed with water.It was shampooed with a 7.5% SLS solution, rinsed and dried. For quickdrying, the tresses were left in the humidity chamber at 20% RelativeHumidity, 50° C. for 20 minutes. Blow drying was avoided so as not toentangle the hair and induce damage. The hair was also sometimesair-dried for at least 3-4 hours. The procedure was repeated up to 3times if triple bleached hair was desired.

Color treatment: The dye bath/paste should be enough to overwhelm thehair and saturate the hair (about 5 gram paste for 1 gram hair). Whenseveral tresses were dyed at the same time, there were delay timesbetween the application of the dyes or shampoos that may cause the tonesand shades of the dyes to be different for each tress. To minimize anydiscrepancy in color, the dye mix was quickly spread over both sides ofthe tress, and the timer started. The dye was then worked through eachtress and sealed in foil as quickly as possible. After the color wasdeveloped (usually for 30 minutes), the tress was thoroughly rinsed.Tresses that had dye worked through them first were rinsed first tominimize timing differences.

Color lastingness: The lastingness of the color was determined throughshampooing. Multiple shampoos may be done in a row without drying inbetween. The wash-out experiments were done in a consistent manner. Theshampoo cycles involved the hair being lathered in a controlled mannerwith a 7.5% (w/w) SLS solution for 15 seconds and rinsed for 15 secondsunder warm water at 35(±5)° C. This process was done 15-25 times tosimulate the number of shampoos during 4-6 weeks after a consumer hasdyed his/her hair.

Performance Evaluation: One gram single bleached hair tresses fromInternational Hair Importers were (a) dyed with a leading commercial reddye or (b) treated with a non-red based commercially available kit for30 minutes at room temperature to “lift” the hair (e.g., make the hairmore porous), followed by soaking in a 0.6% (w/w) solution of compound Ain a 1:1 mixture of EtOH:phosphate buffer, pH 4.5 for 10 minutes at roomtemperature.

Upon conclusion of the color treatment process, the tresses were rinseduntil water runs clear and shampooed and rinsed once. The tresses werethen shampooed, as described above. The results, shown in FIG. 1,demonstrate that tresses dyed with compound A (FIG. 1 b) significantlyresist fading, have a greater color fastness and are brighter than thetresses dyed with the leading commercial red dye (FIG. 1 a) after thesame number of washings.

In a second assay to determine the effect of the dyes of the inventionon damaged hair, virgin medium blond, single bleached (commercial), 3×40V from virgin medium brown, platinum (commercial double bleached), 6×40V from Virgin medium brown, and 9×40 V from virgin medium brown were (a)dyed with either the leading commercially available red dye (1 g of dyecream to 1 mL of 20V peroxide) for 30 minutes at room temperature or (b)treated with a blond commercially available kit such as L'Oréal SuperiorPreference 9½ NB or with a dyeless base prepared on site for 30 minutesat room temperature to “lift” the hair (e.g., make the hair moreporous), followed by soaking in a 0.6% (w/w) solution of compound A in a1:1 mixture of EtOH:phosphate buffer, pH 4.5 for 10 minutes at roomtemperature. The results, shown in FIG. 2, demonstrate that withincreasing damage (moving from left to right across FIG. 2), the leadingcommercial red dye exhibits significant fading and color loss (FIG. 2a). In contrast, the tresses dyed with compound A demonstrated aninverse color fastness to porosity property. That is, with increaseddamage to hair, compound A provided greater deposits of color and agreater color fastness compared to the leading commercially availablered dye on similarly damaged hair.

Example 4 Visual Inspection of Exemplary Dyes of the Invention

To determine the extent of color fastness and vibrancy, a number oftresses are prepared as described above in Example 3. After the tressesare dried, a visual inspection comparing the tresses with controltresses is performed to evaluate vibrancy and color fastness of thedyes. A scale from 1 to 4 is then used to rank the vibrancy and colorfastness compared to the control tresses, as shown below. Additionally,compounds of the present invention were analyzed for color fastness onhair tresses using a Konica Minolta Chroma Meter CR-400 with theSpectraMagic™ NX Lite CM-S100w 1.91.0002 software package and were foundto retain color after multiple shampoo cycles.

Vibrancy Scale 1 = no vibrancy when compared to control 2 = littlevibrancy when compared to control 3 = some vibrancy when compared tocontrol 4 = substantially the same vibrancy when compared to control 5 =greater vibrancy when compared to control

Color Fastness Scale 1 = no no color when compared to control 2 = littlecolor when compared to control 3 = some color when compared to control 4= substantially the same color when compared to control 5 = greatercolor when compared to control

Equivalents

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, many equivalents to the specificembodiments of the invention described herein. Such equivalents areintended to be encompassed by the following claims.

Incorporation by Reference

The contents of all references, patents and patent applications citedthroughout this application are hereby incorporated by reference.

1. A functionalized dye comprising at least one chromophore and a colorfastness moiety, wherein the chromophore is bound to the color fastnessmoiety by a linker, wherein said functionalized dye has an enhancedcolor fastness compared to a non-functionalized direct dye.
 2. The dyeof claim 1, wherein said dye is a compound of formula Ia:C-L-F   (Ia) wherein C is a chromophore; L is a linker; and F is a colorfastness moiety, or a cosmetically acceptable salt thereof.
 3. The dyeof claim 2, wherein the color fastness moiety comprises at least onehydrogen bond donor and at least one hydrogen bond acceptor. 4.(canceled)
 5. The dye of claim 3, wherein the hydrogen bond acceptor isa tertiary amine and the hydrogen bond donor is a secondary amine. 6.(canceled)
 7. The dye of claim 2, wherein C is of formula IIz:

wherein R^(26a) is attached to linker L; and R^(26b), R^(26c), R^(26d),R^(26e) and R^(26f) are each independently are each independentlyhydrogen, hydroxy, amino, alkoxy, alkyl, halogen, NO₂, CF₃, SO₃H, CN,aminocarbonyl, carbonyl, alkoxycarbonyl or an aryldiazene moiety.
 8. Thedye of claim 7, wherein R^(26b) is —NO₂, R^(26c), R^(26e) and R^(26f)are hydrogen and R^(26d) is hydrogen or NH₂.
 9. (canceled) 10.(canceled)
 11. The dye of claim 2, wherein linker L is of formula (III):

wherein L covalently links the chromophore C via the left hand side offormula III to the color fastness moiety F via the right hand side offormula III; a, b, c, d, e, and f are each independently an integer from0-2, provided that at least one of a, b, c, d, e and f is not 0; R⁴⁰,R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰ and R⁵¹ are eachindependently absent or hydrogen; E is NR⁵² or NR⁵³C═O; R⁵² and R⁵³ areeach independently hydrogen or alkyl.
 12. The dye of claim 11, whereina, b, c and d are each 0, e and f are each 1, E is NR⁵² and R⁵² ishydrogen. 13-15. (canceled)
 16. The dye of claim 2, wherein the colorfastness moiety is of formula (Va):

wherein m, n, o, p, q and r are each independently an integer from 0-2,provided that at least one of m, n, o, p, q and r is not 0; R⁷⁸, R⁷⁹,R⁸⁰, R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁷, R⁸⁸ and R⁸⁹ are each independentlyhydrogen or absent; R⁸⁶ is absent, hydrogen or hydroxyl; K is NR⁹⁰,C(═O)NR⁹² or OC═O; W is NR⁹⁵R⁹⁶, CR⁹⁷R⁹⁸R⁹⁹ or OR¹⁰⁰; R⁹⁰ and R⁹² areeach independently hydrogen or alkyl; R⁹⁵ is alkyl and R⁹⁶ is hydrogenor alkyl, or R⁹⁵ and R⁹⁶, together with the nitrogen to which they areattached are linked to form a 4-8-membered heterocyclic ring comprising1-3 heteroatoms; R⁹⁷, R⁹⁸ and R⁹⁹ are hydrogen, alkyl, alkoxy orheteroaryl; and R¹⁰⁰ is hydrogen or alkyl, and provided that when m, n,o and p are 0; q and r are 1, R⁸⁶, R⁸⁷, R⁸⁸ and R⁸⁹ are each hydrogen; Wis OR¹⁰⁰, K is NR⁹⁰ and R¹⁰⁰ is hydrogen, then R⁹⁰ is not methyl. 17.The dye of claim 16 wherein m, n and o are 0, p, q and r are each 1,R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷; R⁸⁸ and R⁸⁹ are each hydrogen, K is NR⁹⁰ and R⁹⁰ ishydrogen. 18-22. (canceled)
 23. The dye of claim 2, wherein the dye is acompound of formula Xa:

wherein R^(a), R^(b), R^(c), R^(d) and R^(e) are each independentlyhydrogen, hydroxy, amino, alkoxy, alkyl, halogen, NO₂, CF₃, SO₃H, CN,aminocarbonyl, carbonyl, alkoxycarbonyl or an aryldiazene moiety; aa andbb are each an integer from 1-5; A is NR^(f) or NR^(f)CO; D is O(CO),NR^(g) or CONR^(g); R^(f), R^(g) and R^(h) are each independentlyhydrogen or alkyl; R^(i) is alkyl; or R^(h) and R^(i) are linkedtogether with the atom to which they are attached form a 4-8 memberedheterocyclic ring with 1-3 heteroatoms; or a cosmetically acceptablesalt thereof.
 24. The dye of claim 23, wherein R^(a) is —NO₂, R^(b),R^(d) and R^(e) are each hydrogen, R^(c) is hydrogen or NH₂, A isNR^(f), D is NR^(g) and R^(f) and R^(g) are each hydrogen. 25-29.(canceled)
 30. The dye of claim 24, wherein R^(h) and R^(i) are eachalkyl.
 31. The dye of claim 30, wherein said alkyl is methyl, ethyl orhydroxyethyl.
 32. The dye of claim 24, wherein R^(h) and R^(i) arelinked to form a 6-membered heterocyclic ring.
 33. The dye of claim 32,wherein said ring is a piperidine or morpholine ring.
 34. The dye ofclaim 23, wherein said dye is a compound of formula (XIa):

R^(j) and R^(k) are each independently hydrogen, hydroxy, amino, alkoxy,alkyl, halogen, NO₂, CF₃, SO₃H, CN, aminocarbonyl, carbonyl,alkoxycarbonyl or an aryldiazene moiety; cc and dd are each an integerfrom 1-5; T is NR^(l) or NR^(l)CO; M is NR^(m) or CONR^(m); R^(l), R^(m)and R^(n) are each independently hydrogen or alkyl; R^(o) is alkyl; orR^(n) and R^(o) are linked together with the atom to which they areattached form a 4-8 membered heterocyclic ring with 1-3 heteroatoms; andcosmetically acceptable salts thereof.
 35. The dye of claim 34, whereinT is NR^(l), M is NR^(m), R^(l) and R^(m) are each hydrogen, cc is 2 anddd is 3, R^(j) is NO₂ and R^(k) is hydrogen or NH₂. 36-40. (canceled)41. The dye of claim 35, wherein R^(n) and R^(o) are each alkyl.
 42. Thedye of claim 41, wherein said alkyl is methyl, ethyl or hydroxyethyl.43. The dye of claim 42, wherein R^(n) and R^(o) are linked to form a6-membered heterocyclic ring.
 44. The dye of claim 43, wherein said ringis a piperidine or morpholine ring.
 45. The dye of claim 34, whereinsaid dye is a compound of formula XII:

wherein R^(p) is hydrogen or amino; R^(q) and R^(r) are eachindependently hydrogen or alkyl; ee and ff are each independently aninteger from 1-5; and R^(s) and R^(t) are each alkyl or together withthe atom to which they are attached form a 4-8 membered heterocyclicring with 1 or 2 heteroatoms, and cosmetically acceptable salts thereof.46. The dye of claim 45, wherein R^(q) and R^(r) are each hydrogen, eeis 2 and ff is 3 and R^(p) is hydrogen or NH₂.
 47. (canceled)
 48. Thedye of claim 46, wherein R^(s) and R^(t) are each alkyl.
 49. The dye ofclaim 48, wherein said alkyl is methyl, ethyl or hydroxyethyl.
 50. Thedye of claim 46, wherein R^(s) and R^(t) are linked to form a 6-memberedheterocyclic ring.
 51. The dye of claim 50, wherein said ring is apiperidine or morpholine ring.
 52. (canceled)
 53. (canceled)
 54. The dyeof claim 45, wherein said dye is a compound of formula XIII:

wherein R^(u) is hydrogen or NH₂ and R^(v) and R^(w) are alkyl, andcosmetically acceptable salts thereof.
 55. The dye of claim 52, whereinR^(v) and R^(w) are each methyl, ethyl or hydroxyethyl.
 56. A dyeselected from:

and cosmetically acceptable salts thereof.
 57. A dye compositioncomprising at least one dye of claim 1 and a medium suitable for dyeingkeratin fibers.
 58. The composition of claim 57, wherein said mediumfurther includes one or more of surfactants, thickeners, fragrances,sequestering agents, UV-screening agents, waxes, silicones, preservingagents, couplers, primary intermediates, alkalizing agents, direct dyes,ceramides, oils, vitamins, provitamins, opacifiers, reducing agents,antioxidants, emulsifiers, stabilizers, solvents, and buffers.
 59. Amethod for coloring hair comprising applying to said hair a dyecomposition comprising at least one dye of claim 1, such that said hairis colored.
 60. The method of claim 59, wherein said coloring hair ishighlighting hair or touching up roots.
 61. A kit comprising a dyecomposition comprising at least one dye of claim 1 and instructions foruse.